JP4441369B2 - Silver halide photographic material - Google Patents

Description

  The present invention relates to a silver halide photographic light-sensitive material. More specifically, the present invention relates to a silver halide photographic light-sensitive material, and more particularly, there is little desensitization failure of the light-sensitive material due to adhesion of water-insoluble matter in a developing solution, and storage stability (when stored under high humidity). The present invention relates to a silver halide photographic light-sensitive material having excellent sensitivity reduction.

  In recent years, higher sensitivity has been demanded for enhancing the user benefit of silver halide photographic light-sensitive materials, and a significant increase in sensitivity has been achieved through extensive research. However, the high-sensitivity photosensitive material is sensitive to light emission generated when a photosensitive material charged during the manufacturing, photographing or developing process of the photosensitive material is discharged with another object. Therefore, it has been desired to improve the chargeability of the photosensitive material. For this reason, a fluorosurfactant is often added to the photosensitive material for the purpose of aligning the surface of the photosensitive material and adjusting the chargeability (see, for example, Patent Document 1).

  At this time, since the fluorosurfactant is dissolved in a very small amount in water or a hydrophilic organic solvent, it is often the case that a hydrocarbon surfactant is added simultaneously for the purpose of solubilizing the fluorosurfactant. (For example, refer to Patent Document 2).

  On the other hand, when the surfactant added to the photosensitive material forms a complex with low solubility in water, it is known that the photosensitive material is attached with dust to which water-insoluble matter in the developing solution adheres during development processing. . Accordingly, it has been proposed to prevent a desensitization failure of the photosensitive material due to adhesion of water insoluble matter by selecting an appropriate surfactant (see, for example, Patent Document 3). However, according to this technique, there is a problem that sensitivity is greatly reduced when stored under high humidity and storage stability is lacking.

In this way, both the desensitization failure of the photosensitive material due to the adhesion of water-insoluble matter in the developing solution and the excellent storage stability (particularly the decrease in sensitivity when stored under high humidity) are obtained. Satisfactory silver halide photographic materials have not been provided.
JP 2003-114503 A JP 2003-270754 A JP 2004-77531 A

  The object of the present invention is that there is little desensitization failure of the photosensitive material due to adhesion of water-insoluble matter in the developing solution, and excellent storage stability (more specifically, less sensitivity decrease when stored under high humidity). Another object is to provide a silver halide photographic light-sensitive material.

As a result of the diligent efforts of the present inventors, it has been found that the above problems can be solved by the following means.
(1) In a silver halide photographic light-sensitive material having one or more layers including at least one photosensitive layer on a support, at least one of at least one of the layers formed on the support And a fluorine-containing surfactant (hereinafter referred to as “fluorine-based surfactant of the present invention”) in at least one of the layers formed on the support. A silver halide photographic light-sensitive material, characterized by comprising:

General formula (1)
^{_{R 1 -L-C m H 2m}} -Z
[Wherein, R ¹ represents a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms or a substituted or unsubstituted alkenyl group, and L represents —O—, —NH—, —COO—, or —CONH— . . m represents an integer of 2 to 6. Z represents OSO ₃ M or SO ₃ M, and M represents an alkali metal, a hydrogen atom, ammonium or alkylammonium. ]

  (2) The silver halide photographic light-sensitive material as described in (1), wherein the fluorine-based surfactant is a compound represented by any one of the following general formulas (2A) to (2D).

General formula (2A)

[Wherein, R ^A1 and R ^A2 each independently represents a substituted or unsubstituted alkyl group, and at least one of R ^A1 and R ^A2 represents an alkyl group substituted with a fluorine atom. R ^A3 , R ^A4 and R ^A5 each independently represent a hydrogen atom or a substituent, L ^A1 , L ^A2 and L ^A3 each independently represent a single bond or a divalent linking group, and X ⁺ represents a cationic substituent. Represents a group. Y ⁻ represents a counter anion, but Y ⁻ may not be present when the charge is 0 in the molecule. m ^A represents 0 or 1. ]

General formula (2B)

[Wherein, R ^B3 , R ^B4 and R ^B5 each independently represent a hydrogen atom or a substituent. A and B each independently represent a fluorine atom or a hydrogen atom. n ^B3 and n ^B4 each independently represents an integer of 4 to 8. L ^B1 and L ^B2 each independently represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group formed by combining these. m ^B represents 0 or 1. M represents a cation. ]

General formula (2C)

[Wherein R ^C1 represents a substituted or unsubstituted alkyl group, and R ^CF represents a perfluoroalkylene group. A represents a hydrogen atom or a fluorine atom, and L ^C1 represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group formed by combining these. One of Y ^C1 and Y ^C2 represents a hydrogen atom, and the other represents -L ^C2 -SO ₃ M, and L ^C2 represents a single bond or a substituted or unsubstituted alkylene group. M represents a cation. ]

General formula (2D)
[Rf ^D- (L ^D ) _nD ] _mD -W
[Wherein Rf ^D represents a perfluoroalkyl group, L ^D represents an alkylene group, W represents an anionic group, a cationic group, a betaine group or a nonionic polar group necessary for imparting surface activity. Represents a group having n ^D represents an integer of 0 or 1, m ^D represents an integer of 1-3. ]

(3) The halogen according to (1) or (2), wherein the layer located farthest from the support on the side having the photosensitive layer contains the compound represented by the general formula (1) Silver halide photographic material.
(4) Any one of (1) to (3), wherein the fluorine-containing surfactant is contained in the same layer as the layer containing the compound represented by the general formula (1). The silver halide photographic light-sensitive material described in 1.
(5) The silver halide photographic light-sensitive material as described in any one of (1) to (4), wherein the silver halide photographic light-sensitive material is a silver halide color photographic light-sensitive material.

  According to the present invention, a halogen which is less susceptible to desensitization of a light-sensitive material due to adhesion of a water-insoluble substance in a developing solution and has excellent storage stability (more specifically, a decrease in sensitivity when stored under high humidity) A silver halide photographic light-sensitive material can be provided.

  The silver halide photographic light-sensitive material of the present invention will be described in detail below. The embodiment of the silver halide photographic light-sensitive material of the present invention is arbitrary, and application to any silver halide photographic light-sensitive material regardless of positive type or negative type is effective. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

The silver halide photographic light-sensitive material of the present invention contains a compound represented by the following general formula (1).
General formula (1)
^{_{R 1 -L-C m H 2m}} -Z
In the formula, R ¹ represents an alkyl group or alkenyl group having 1 to 5 carbon atoms. The number of carbon atoms in R ¹ is preferably 1 to 5, more preferably 1 to 4, 2 to 4 are particularly preferred. The alkyl group and the alkenyl group may have a cyclic structure (that is, a cycloalkyl group or a cycloalkenyl group), but a chain alkyl group and a chain alkenyl group are more preferable. The alkyl group and alkenyl group may have a substituent, but are preferably unsubstituted alkyl groups and alkenyl groups. The chain alkyl group and the chain alkenyl group may have a branch. The position of the double bond of the alkenyl group is not particularly limited. Alkyl groups are preferred over alkenyl groups.

L is, -O -, - NH -, - COO- or -CONH- represents, -O -, - COO-, but good Mashiku, -O- is particularly preferred.
m represents an integer of 2 to 6, 2 to 5 is more preferable, and 3 to 4 is particularly preferable. -C _m H _2m - may be a chain have a branch.
Z represents OSO ₃ M and SO ₃ M. M represents an alkali metal, a hydrogen atom, ammonium or alkylammonium, preferably an alkali metal or ammonium, and more preferably an alkali metal (particularly Na or K).

  Specific examples of the compound represented by the general formula (1) are shown below, but the compound represented by the general formula (1) that can be used in the present invention is not limited thereto.

_{W-1 C 4 H 9 -O-} (CH 2) 4 -SO 3 Na
_{W-2 C 5 H 11 -O-} (CH 2) 4 -SO 3 Na
_{W-3 C 4 H 9 -O-} (CH 2) 3 -SO 3 Na
_{W-4 CH 2 = CHCH 2} CH 2 -O- (CH 2) 3 -SO 3 Na
_{W-5 CH 2 = CHCH 2} CH 2 -O- (CH 2) 4 -SO 3 Na
_{W-6 CH 3 -O- (CH} 2) 4 -SO 3 K
_{W-7 C 2 H 5 -O-} (CH 2) 4 -SO 3 Na
_{W-8 C 3 H 7 -O-} (CH 2) 4 -SO 3 Na
_{W-9 C 5 H 11 -O-} (CH 2) 4 -SO 3 Na
_{W-10 CH 2 = CHCH 2} -O- (CH 2) 4 -SO 3 NH 4
_{W-11 CH 3 CH = CHCH} 2 -O- (CH 2) 4 -SO 3 Na
_{W-12 C 4 H 9 -O} -CH 2 CH (CH 3) -OSO 3 Na
_{W-13 C 5 H 11 -O} -CH 2 CH (CH 3) -OSO 3 Na
_{W-14 C 4 H 9 -O} -CH (CH 3) CH 2 -OSO 3 Na
_{W-15 C 3 H 7 -O} -CH 2 CH (CH 3) -OSO 3 Na
_{W-16 CH 3 -O-CH} 2 CH (CH 3) -OSO 3 K
_{W-17 C 2 H 5 -O} -CH 2 CH (CH 3) -OSO 3 Na
_{W-18 CH 2 = CHCH 2} CH 2 -O-CH 2 CH (CH 3) -OSO 3 Na
_{W-19 C 3 H 7 -O} -CH (CH 3) CH 2 -OSO 3 Na
_{W-20 CH 2 = CHCH 2} -O- (CH 2) 2 -OSO 3 NH 4
W-21 C ₄ H ₉ —O— (CH ₂ ) ₃ —OSO ₃ Na
_{W-22 C 4 H 9 -O-} (CH 2) 4 -OSO 3 Na
_{W-23 C 4 H 9 -O-} (CH 2) 2 -OSO 3 Na
_{W-24 C 4 H 9 -NH-} (CH 2) 3 -OSO 3 Na
_{W-25 C 4 H 9 -COO-} (CH 2) 2 -OSO 3 Na
_{W-26 CH 3 -NH- (CH} 2) 4 -OSO 3 K
_{W-27 C 2 H 5 -COO-} (CH 2) 4 -OSO 3 Na
_{W-28 C 3 H 7 -COO-} (CH 2) 4 -OSO 3 Na
_{W-29 C 5 H 11 -NH-} (CH 2) 4 -OSO 3 Na
_{W-30 CH 2 = CHCH 2} -COO- (CH 2) 4 -OSO 3 NH 4
_{W-31 C 4 H 9 -NH} -CH 2 CH (CH 3) -OSO 3 Na
_{W-32 C 2 H 5 -NH-} (CH 2) 3 -OSO 3 K
_{W-33 CH 3 -CONH- (CH} 2) 3 -OSO 3 Na
_{W-35 C 4 H 9 -NH-} (CH 2) 2 -OSO 3 Na
_{W-36 C 3 H 7 -O-} (CH 2) 5 -OSO 3 Na
_{W-37 CH 3 -O- (CH} 2) 6 -OSO 3 Na

  The compound represented by the general formula (1) is described in J. Phys. Chem. 90, 2413 (1986), J. Dispersion Sci. And Tech., 4,361 (1983), US Pat. No. 5,602,087. It can be synthesized by a known method described in a book. For specific procedures, reference can be made to Synthesis Examples 1 and 2 described later.

  The compound represented by the general formula (1) is preferably added to various photographic coating solutions in the range of 0.001% by mass to 5% by mass, more preferably 0.01% by mass to 1.0% by mass. Preferably, 0.02% by mass to 0.5% by mass is particularly preferable. The layer coated with the coating liquid containing the compound represented by the general formula (1) is preferably milked with the fluorosurfactant of the present invention. If the fluorine-containing surfactant of the present invention is contained in a sufficient amount in the layer containing the compound represented by the general formula (1), it is possible to more effectively prevent adhesion of water-insoluble substances in the developing solution, The applicability can be further improved.

  Each of the compounds represented by the general formula (1) may be used alone, or a plurality of different compounds may be used. In the case of using a plurality of different compounds, a plurality of compounds may be used in the same layer, or each compound may be used alone in a plurality of layers.

  The layer to which the compound represented by the general formula (1) is added is preferably the uppermost layer located farthest from the support in order to reduce undesirable side effects. You may add to the layer which has, and an intermediate | middle layer. Preferred is an embodiment in which the most distribution is made in the uppermost layer located farthest from the support. Moreover, the compound represented by General formula (1) may be added to several layers, and may be added only to any one layer.

Next, the fluorine-based surfactant that can be used in the silver halide photographic light-sensitive material of the present invention (fluorine-based surfactant of the present invention) will be described in detail.
The fluorosurfactant of the present invention is preferably contained in the silver halide photographic light-sensitive material in an amount of 40 mg / m ² or more, more preferably 45 mg / m ² or more, and particularly preferably 50 mg / m ² or more. preferable.

  Each of the fluorosurfactants of the present invention may be used alone, or a plurality of different compounds may be used. In the case of using a plurality of different compounds, a plurality of compounds may be used in the same layer, or each compound may be used alone in a plurality of layers.

  In order to reduce undesirable side effects, the layer to which the fluorosurfactant of the present invention is added is preferably the uppermost layer located farthest from the support, but other layers having spectral sensitivity other than It may be added to the intermediate layer. Preferred is an embodiment in which the most distribution is made in the uppermost layer located farthest from the support. Moreover, the fluorine-type surfactant of this invention may be added to several layers, and may be added only to any one layer.

  The content ratio of the fluorosurfactant of the present invention to the compound represented by the general formula (1) in the silver halide photographic light-sensitive material of the present invention is 0 with respect to 1 mol of the compound represented by the general formula (1). It is preferably 0.001 to 100 mol, more preferably 0.005 to 50 mol, and still more preferably 0.01 to 25 mol.

  Examples of the fluorine-based surfactant include compounds represented by the following general formulas (2A) to (2D). The general formulas (2A) to (2D) will be described in detail below in order.

General formula (2A)

In the formula, R ^A1 and R ^A2 each independently represent a substituted or unsubstituted alkyl group, and at least one of R ^A1 and R ^A2 represents an alkyl group substituted with a fluorine atom. R ^A3 , R ^A4 and R ^A5 each independently represent a hydrogen atom or a substituent, L ^A1 , L ^A2 and L ^A3 each independently represent a single bond or a divalent linking group, and X ⁺ represents a cationic substituent. Represents a group. Y ⁻ represents a counter anion, but Y ⁻ may not be present when the charge is 0 in the molecule. m ^A represents 0 or 1.

In the general formula (2A), R ^A1 and R ^A2 each independently represent a substituted or unsubstituted alkyl group. The alkyl group has 1 or more carbon atoms and may be linear, branched or cyclic. Examples of the substituent include a halogen atom, an alkenyl group, an aryl group, an alkoxyl group, a halogen atom other than fluorine, a carboxylic acid ester group, a carbonamido group, a carbamoyl group, an oxycarbonyl group, and a phosphoric acid ester group. However, at least one of R ^A1 and R ^A2 represents an alkyl group substituted with a fluorine atom (hereinafter, the alkyl group substituted with a fluorine atom is referred to as “Rf”).

  Rf is an alkyl group substituted with at least one fluorine atom having 1 or more carbon atoms. Rf only needs to be substituted with at least one fluorine atom, and may have any of linear, branched and cyclic structures. Further, it may be further substituted with a substituent other than a fluorine atom, or may be substituted only with a fluorine atom. Examples of the substituent other than the fluorine atom of Rf include an alkenyl group, an aryl group, an alkoxyl group, a halogen atom other than fluorine, a carboxylic acid ester group, a carbonamido group, a carbamoyl group, an oxycarbonyl group, and a phosphoric acid ester group.

Rf is preferably a fluorine-substituted alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 4 to 10 carbon atoms. Preferred examples of Rf include the following.
_{- (CH 2) 2 - (} CF 2) 4 F,
_{- (CH 2) 2 - (} CF 2) 6 F,
_{- (CH 2) 2 - (} CF 2) 8 F,
_{- (CH 2) - (CF} 2) 4 H,
_{- (CH 2) - (CF} 2) 6 H,
_{- (CH 2) - (CF} 2) 8 H,
_{- (CH 2) 3 - (} CF 2) 4 F,
_{- (CH 2) 6 - (} CF 2) 4 F,
-CH (CF ₃₎ CF _3,

Rf is more preferably an alkyl group having 4 to 10 carbon atoms, the terminal of which is substituted with a trifluoromethyl group, and particularly preferably 3 to 3 carbon atoms represented by — (CH ₂ ) α- (CF ₂ ) βF. 10 represents an alkyl group (α represents an integer of 1 to 6; β represents an integer of 3 to 8). Specifically, the following are mentioned.
_{-CH 2 - (CF 2) 2} F,
_{- (CH 2) 6 - (} CF 2) 4 F,
_{- (CH 2) 3 - (} CF 2) 4 F,
_{-CH 2 - (CF 2) 3} F,
_{- (CH 2) 2 - (} CF 2) 4 F,
_{- (CH 2) 3 - (} CF 2) 4 F,
_{- (CH 2) 6 - (} CF 2) 4 F,
_{- (CH 2) 2 - (} CF 2) 6 F,
_{- (CH 2) 3 - (} CF 2) 6 F,
_{- (CH 2) 2 - (} CF 2) 6 F,
Among these, in _{particular, - (CH 2) 2 -} (CF 2) 4 F and _{- (CH 2) 2 - (} CF 2) 6 F is preferred.

In the general formula (2A), both R ^A1 and R ^A2 preferably represent Rf.

When R ^A1 and R ^A2 each represents an alkyl group other than Rf, that is, an alkyl group not substituted with a fluorine atom, the alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, A substituted or unsubstituted alkyl group having 6 to 24 carbon atoms is more preferable. Preferred examples of the unsubstituted alkyl group having 6 to 24 carbon atoms include n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1, 3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, eicosyl group, 2-octyldodecyl group, docosyl group, tetracosyl group, 2-decyltetra A decyl group, a tricosyl group, a cyclohexyl group, a cycloheptyl group, etc. are mentioned. Preferred examples of the alkyl group having 6 to 24 carbon atoms having a substituent include 2-hexenyl group, oleyl group, linoleyl group, linolenyl group, benzyl group, β-phenethyl group, 2-methoxyethyl group, 4-phenylbutyl group, 4-acetoxyethyl group, 6-phenoxyhexyl group, 12-phenyldodecyl group, 18-phenyloctadecyl group, 12- (p-chlorophenyl) dodecyl group, 2- (diphenyl phosphate) ethyl group, etc. Can be mentioned.

The alkyl group other than Rf represented by R ^A1 and R ^A2 is more preferably a substituted or unsubstituted alkyl group having 6 to 18 carbon atoms. Preferred examples of the unsubstituted alkyl group having 6 to 18 carbon atoms include n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3- Examples include trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, 4-tert-butylcyclohexyl group and the like. Preferable examples of the substituted alkyl group having 6 to 18 carbon atoms having a substituent include phenethyl group, 6-phenoxyhexyl group, 12-phenyldodecyl group, oleyl group, linoleyl group, and linolenyl group. .

The alkyl group other than Rf represented by R ^A1 and R ^A2 is particularly preferably an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, oleyl group, linoleyl group, linolenyl group, most preferably carbon It is a linear, cyclic or branched unsubstituted alkyl group of formula 8-16.

In the general formula (2A), R ^A3 , R ^A4 and R ^A5 each independently represent a hydrogen atom or a substituent. Substituent T described later can be applied as the substituent.
R ^A3 , R ^A4 and R ^A5 preferably represent an alkyl group or a hydrogen atom, more preferably represent an alkyl group having 1 to 12 carbon atoms or a hydrogen atom, and more preferably represent a methyl group or a hydrogen atom. And particularly preferably represents a hydrogen atom.

In the general formula (2A), L ^A1 and L ^A2 each independently represent a single bond or a divalent linking group. There is no particular limitation as long as it is a single bond or a divalent linking group, but preferably an arylene group, —O—, —S— or —NR ^A100 — (R ^A100 represents a hydrogen atom or a substituent. R ^A100 is the same as the substituent T described later, preferably an alkyl group, the aforementioned Rf or hydrogen atom, and more preferably a hydrogen atom), or a group obtained by combining them. Preferred is —O—, —S— or —NR ^A100 —. L ^A1 and L ^A2 are more preferably —O— or —NR ^A100 —, more preferably —O— or —NH—, and particularly preferably —O—.

In the general formula (2A), L ^A3 represents a divalent linking group. The divalent linking group is not particularly limited, but is preferably an alkylene group, an arylene group, -C (= O)-, -O-, -S-, -S (= O)-, -S (= O) ₂ — or —NR ^A100 — (R ^A100 represents a hydrogen atom or a substituent, and the substituent is the same as the later-described substituent T. R ^A100 is preferably an alkyl group or a hydrogen atom, more preferably Is a hydrogen atom) alone or in combination thereof, more preferably an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, -C (= O)-, -O —, —S—, —S (═O) —, —S (═O) ₂ — or —NR ^A100 — is a group obtained alone or in combination. More preferably, Z is an alkylene group having 1 to 8 carbon atoms, —C (═O) —, —O—, —S—, —S (═O) —, —S (═O) ₂ — or —NR. ^A100- is a group obtained by singly or in combination, and examples thereof include the following.
- (CH _{2) 2} S-,
- (CH _{2) 2} NH-,
- (CH _{2) 3} NH-,
_{- (CH 2) 2 C (} = O) NH-,
_{- (CH 2) 2 SCH 2} -,
_{- (CH 2) 2 NHCH 2} -,
_{- (CH 2) 3 NHCH 2} -,

In the general formula (2A), X ⁺ represents a cationic substituent, and X ⁺ is preferably an organic cationic substituent, and more preferably a nitrogen or phosphorus cationic group. More preferred is a pyridinium cation or an ammonium cation, and more preferred is a trialkylammonium cation represented by the following general formula (3).

General formula (3)

In the general formula (3), R ^A13 , R ^A14 and R ^A15 each independently represents a substituted or unsubstituted alkyl group. As the substituent, those exemplified as the substituent T described later can be applied. R ^A13 , R ^A14 and R ^A15 may combine with each other to form a ring, if possible. R ^A13 , R ^A14 and R ^A15 are preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group, an ethyl group or a methyl carboxyl group. And particularly preferably a methyl group.

In the general formula (3), Y ⁻ represents a counter anion and may be an inorganic anion or an organic anion. Further, when the charge becomes 0 in the molecule, Y ⁻ may not be present. Preferred examples of the inorganic anion include iodo ion, bromine ion and chlorine ion, and preferred examples of the organic anion include p-toluenesulfonate ion and benzenesulfonate ion. Y ^- is more preferably iodo ion, p-toluenesulfonic acid ion or benzenesulfonic acid ion, and further preferably p-toluenesulfonic acid.
In the general formula (2A), m ^A represents 0 or 1, preferably 0.

  Among the compounds represented by the general formula (2A), a compound represented by the following general formula (2A-1) is preferable.

General formula (2A-1)

In General Formula (2A-1), R ^A11 and R ^A12 each independently represent a substituted or unsubstituted alkyl group, and at least one of R ^A11 and R ^A12 represents an alkyl group substituted with a fluorine atom, The total number of carbon atoms of R ^A11 and R ^A12 is 19 or less. L ^A2 and L ^A3 each independently represent —O—, —S—, or —NR ¹⁰⁰ —, R ¹⁰⁰ represents a hydrogen atom or a substituent, and L ^A1 represents a single bond or a divalent linking group. L ^A1 and Y ⁻ have the same meanings as those in the general formula (2A), and preferred ranges thereof are also the same. R ^A13 , R ^A14 and R ^A15 have the same ^{meanings as} those in the general formula (3), and preferred ranges thereof are also the same.

In the general formula (2A-1), L ^A2 and L ^A3 each independently represent —O—, —S—, or —NR ¹⁰⁰ — (R ¹⁰⁰ represents a hydrogen atom or a substituent, and the substituent is described later. Those listed as the substituent T can be applied, and R ¹⁰⁰ is preferably an alkyl group, the aforementioned Rf, or a hydrogen atom, and more preferably a hydrogen atom. L ^A2 and L ^A3 are more preferably —O— or —NH—, and still more preferably —O—.

In the general formula (2A-1), R ^A11 and R ^A12 have the same ^{meanings as} R ^A1 and R ^A2 in the general formula (2A), respectively, and preferred ranges thereof are also the same. However, the total number of carbon atoms of R ^A11 and R ^A12 is 19 or less.

  Among the compounds represented by the general formula (2), a compound represented by the following general formula (2A-2) is more preferable.

General formula (2A-2)

In the general formula (2A-2), R ^A13 , R ^A14 , R ^A15 , L ^A1 and Y ⁻ have the same ^{meanings as those in} the general formula (2A) and the general formula (3), respectively, and preferred ranges thereof are also the same. It is. A and B each independently represent a fluorine atom or a hydrogen atom. A and B both preferably represent a fluorine atom or a hydrogen atom, and preferably both represent a fluorine atom.
In the general formula (2A-2), n ^A1 represents an integer of 1 to 6, and n ^A2 represents an integer of 3 to 8.

  Among the compounds represented by the general formula (2A), a compound represented by the following general formula (2A-3) is more preferable.

General formula (2A-3)

In the general formula (2A-3), n ^A1 represents any integer of 1 to 6, n ^A2 represents any integer of 3 to 8, but 2 (n ^A1 + n ^A2 ) is 19 or less. . R ^A13 , R ^A14 , R ^A15 , L ^A1 and Y ⁻ have the same ^{meanings as those in} the general formula (2A) and the general formula (3), respectively, and preferred ranges thereof are also the same.

n ^A1 represents any integer of 1 to 6, preferably an integer of 1 to 3, more preferably 2 or 3, and most preferably 2. n ^A2 represents an integer of 3 to 8, more preferably 3 to 6, and still more preferably 4 to 6. As a preferable combination of n ^A1 and n ^A2 , n ^A1 is preferably 2 or 3, and n ^A2 is preferably 4 or 6.

  Specific examples of the compound represented by the general formula (2A) are shown below, but the compound represented by the general formula (2A) that can be used in the present invention is not limited by the following specific examples. Absent. Unless otherwise specified, the alkyl group and the perfluroalkyl group mean a straight chain structure in the structure notation of the exemplified compounds below. Of the abbreviations in the notation, 2EH means 2-ethylhexyl and 2BO means 2-butyloctyl.

  The compound represented by the general formula (2A) can be synthesized using a fumaric acid derivative, a maleic acid derivative, an itaconic acid derivative, a glutamic acid derivative, an aspartic acid derivative, or the like as a raw material. For example, when a fumaric acid derivative, a maleic acid derivative, or an itaconic acid derivative is used as a raw material, the double bond is subjected to Michael addition reaction with a nucleophilic species and then cationized with an alkylating agent. be able to. For a specific synthesis example, a synthesis example 3 described later can be referred to.

  Next, the compound represented by the following general formula (2B) will be described in detail.

General formula (2B)

In the general formula (2B), R ^B3 , R ^B4 and R ^B5 each independently represent a hydrogen atom or a substituent. A and B each independently represent a fluorine atom or a hydrogen atom. n ^B3 and n ^B4 each independently represents an integer of 4 to 8. L ^B1 and L ^B2 each independently represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group formed by combining these. m ^B represents 0 or 1. M represents a cation.

In the general formula (2B), R ^B3 , R ^B4 and R ^B5 each independently represent a hydrogen atom or a substituent. Substituent T described later can be applied as the substituent.
R ^B3 , R ^B4 and R ^B5 are preferably an alkyl group or a hydrogen atom, more preferably an alkyl group having 1 to 12 carbon atoms or a hydrogen atom, still more preferably a methyl group or a hydrogen atom, Preferably it is a hydrogen atom.

  In the general formula (2B), A and B each independently represent a fluorine atom or a hydrogen atom. A and B are preferably both fluorine atoms or both hydrogen atoms, more preferably both fluorine atoms.

In the general formula (2B), n ^B3 and n ^B4 each independently represents an integer of 4 to 8. n ^B3 and n ^B4 are preferably any integer of 4 to 6, and n ^B3 = n ^B4 , more preferably an integer of 4 or 6, and n ^B3 = n ^B4 , more preferably n ^B3 = n ^B4 = 4.

In the general formula (2B), m ^B represents 0 or 1, both of which are likewise preferred.

In the general formula (2B), L ^B1 and L ^B2 each independently represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent group formed by combining these. As the substituent, the substituent T described later can be applied. L ^B1 and L ^B2 each preferably have 4 or less carbon atoms, and are preferably unsubstituted alkylene.

  M represents a cation and has the same meaning as M in the general formula (1). M is preferably lithium ion, sodium ion, potassium ion or ammonium ion, and more preferably lithium ion, sodium ion or potassium ion. More preferred is sodium ion.

  Among the compounds represented by the general formula (2B), compounds represented by the following general formula (2B-1) are preferable.

General formula (2B-1)

In the general formula (2B-1), R ^B3 , R ^B4 , R ^B5 , n ^B3 , n ^B4 , m ^B , A, B and M have the same meaning as those in the general formula (2B) and are preferable. The range is the same. n ^B1 and n ^B2 each independently represent an integer of 1 to 6.

In the general formula (2B-1), n ^B1 and n ^B2 each independently represents an integer of 1 to 6. n ^B1 and n ^B2 in integer of 1 to 6, and is preferably an n ^B1 = n ^B2, 2 or 3, and more preferably from ^{n B1 = n B2, n B1} = n B2 = 2 More preferably.

  Among the compounds represented by the general formula (2B), a compound represented by the following general formula (2B-2) is more preferable.

General formula (2B-2)

In the general formula (2B-2), n ^B3 , n ^B4 , m ^B and M have the same meanings as those in the general formula (2B), and preferred ranges are also the same. In the general formula (2B-2), n ^B1 and n ^B2 have the same ^{meanings as those} in the general formula (2B-1), and preferred ranges are also the same.

  The compound represented by the general formula (2B) is more preferably a compound represented by the following general formula (2B-3).

General formula (2B-3)

In the general formula (2B-3), n ^B5 represents 2 or 3, and n ^B6 represents any integer of 4 to 6. m ^B represents 0 or 1, both of which are likewise preferred. M has the same meaning as M in the general formula (2B), and the preferred range is also the same.

  Specific examples of the compound represented by the general formula (2B) are shown below, but the compound represented by the general formula (2B) that can be used in the present invention is not limited by the following specific examples. Absent.

  The compound represented by the general formula (2B) can be easily synthesized by combining a general esterification reaction and a sulfonation reaction. The counter cation can be easily converted with an ion exchange resin. For specific synthesis methods, reference can be made to Synthesis Examples 4 and 5 described later.

  Next, the compound represented by the following general formula (2C) will be described in detail.

General formula (2C)

In the general formula (2C), R ^C1 represents a substituted or unsubstituted alkyl group, and R ^CF represents a perfluoroalkylene group. A represents a hydrogen atom or a fluorine atom, and L ^C1 represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group formed by combining these. One of Y ^C1 and Y ^C2 represents a hydrogen atom, the other represents -L ^C2 -SO ₃ M, and M represents a cation.

In the general formula (2C), R ^C1 represents a substituted or unsubstituted alkyl group. The substituted or unsubstituted alkyl group represented by R ^C1 may be linear, branched, or have a cyclic structure. Substituent T described later can be applied as the substituent. Preferred examples of the substituent include alkenyl groups, aryl groups, alkoxy groups, halogen atoms (preferably Cl), carboxylic acid ester groups, carbonamido groups, carbamoyl groups, oxycarbonyl groups, and phosphoric acid ester groups.
R ^C1 is preferably an unsubstituted alkyl group, R ^C1 is more preferably an unsubstituted alkyl group having 2 to 24 carbon atoms, still more preferably an unsubstituted alkyl group having 4 to 20 carbon atoms, and particularly preferably Is an unsubstituted alkyl group having 6 to 24 carbon atoms.

R ^CF represents a perfluoroalkylene group. Here, the perfluoroalkylene group refers to a group in which all hydrogen atoms of the alkylene group are fluorine-substituted. The perfluoroalkylene group may be linear or branched, and may have a cyclic structure. R ^CF preferably has 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms.

  A represents a hydrogen atom or a fluorine atom, and is preferably a fluorine atom.

L ^C1 represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent group formed by combining these. The substituent is the same as the preferred range of the substituent mentioned for R ^C1 . L ^C1 preferably has 4 or less carbon atoms, and is preferably unsubstituted alkylene.

One of Y ^C1 and Y ^C2 represents a hydrogen atom, the other represents -L ^C2 -SO ₃ M, and M represents a cation. Here, preferable examples of the cation represented by M include alkali metal ions (lithium ions, sodium ions, potassium ions, etc.), alkaline earth metal ions (barium ions, calcium ions, etc.), ammonium ions, and the like. . Of these, lithium ions, sodium ions, potassium ions, or ammonium ions are more preferable, and lithium ions, sodium ions, or potassium ions are more preferable. The total number of carbon atoms and substituents of the compound of the general formula (2C) The alkyl group can be appropriately selected depending on the degree of branching of the alkyl group. When the total number of carbon atoms of R ^C1 , R ^CF and L ^C1 is 16 or more, lithium ions are excellent in terms of compatibility between solubility (particularly against water) and antistatic ability or coating uniformity. .
L ^C2 represents a single bond or a substituted or unsubstituted alkylene group. The substituent is the same as the preferred range of the substituent mentioned for R ^C1 .
L ^C2 is preferably a single bond or an alkylene group having 2 or less carbon atoms, more preferably a single bond or an unsubstituted alkylene group, and still more preferably a single bond or a methylene group. L ^C2 is particularly preferably a single bond.

  Among the compounds represented by the general formula (2C), a compound represented by the following general formula (2C-1) is preferable.

General formula (2C-1)

In the general formula (2C-1), R ^C11 represents a substituted or unsubstituted alkyl group having a total carbon number of 6 or more. R ^CF1 represents a perfluoroalkyl group having 6 or less carbon atoms. One of Y ^C11 and Y ^C12 represents a hydrogen atom, the other represents SO ₃ M ^C , and M ^C represents a cation. n ^C1 represents an integer of 1 or more.

In the general formula (2C-1), R ^C11 represents a substituted or unsubstituted alkyl group having 6 or more carbon atoms in total. However, R ^C11 does not become an alkyl group substituted with a fluorine atom. The substituted or unsubstituted alkyl group represented by R ^C11 may be linear, branched, or have a cyclic structure. Examples of the substituent include alkenyl groups, aryl groups, alkoxy groups, halogen atoms other than fluorine, carboxylic acid ester groups, carbonamido groups, carbamoyl groups, oxycarbonyl groups, and phosphoric acid ester groups.

The substituted or unsubstituted alkyl group represented by R ^C11 preferably has 6 to 24 carbon atoms in total. Preferred examples of the unsubstituted alkyl group having 6 to 24 carbon atoms include n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1, 3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, eicosyl group, 2-octyldodecyl group, docosyl group, tetracosyl group, 2-decyltetra A decyl group, a tricosyl group, a cyclohexyl group, a cycloheptyl group, etc. are mentioned. In addition, preferable examples of the substituted alkyl group having 6 to 24 carbon atoms including the carbon atoms of the substituent include 2-hexenyl group, oleyl group, linoleyl group, linolenyl group, benzyl group, β-phenethyl group, 2- Methoxyethyl group, 4-phenylbutyl group, 4-acetoxyethyl group, 6-phenoxyhexyl group, 12-phenyldodecyl group, 18-phenyloctadecyl group, 12- (p-chlorophenyl) dodecyl group, 2- (diphenyl phosphate) An ethyl group etc. can be mentioned.

The substituted or unsubstituted alkyl group represented by R ^C11 preferably has a total carbon number of 6 to 18. Preferred examples of the unsubstituted alkyl group having 6 to 18 carbon atoms include n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3- Examples include trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, 4-tert-butylcyclohexyl group and the like. In addition, preferable examples of the substituted alkyl group having 6 to 18 carbon atoms in total including the carbon number of the substituent include phenethyl group, 6-phenoxyhexyl group, 12-phenyldodecyl group, oleyl group, linoleyl group, linolenyl group and the like. Is mentioned. Among them, as R ^C11 , n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group, It is more preferably n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, oleyl group, linoleyl group, linolenyl group, and linear, cyclic or branched unsubstituted having 8 to 16 carbon atoms. Particularly preferred is an alkyl group.

In the general formula (2C-1), R ^CF1 represents a perfluoroalkyl group having 6 or less carbon atoms. Here, the perfluoroalkyl group refers to a group in which all hydrogen atoms of the alkyl group are substituted with fluorine. The alkyl group in the perfluoroalkyl group may be linear or branched, and may have a cyclic structure. Examples of the perfluoroalkyl group represented by R ^CF1 include trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoroisopropyl group, nonafluoro-n-butyl group, undecafluoro-n. -Pentyl group, tridecafluoro-n-hexyl group, undecafluorocyclohexyl group and the like. Among these, a perfluoroalkyl group having 2 to 4 carbon atoms (for example, a pentafluoroethyl group, a heptafluoro-n-propyl group, a heptafluoroisopropyl group, a nonafluoro-n-butyl group, etc.) is preferable, and heptafluoro-n-propyl. The group, nonafluoro-n-butyl group is particularly preferred.

In the general formula (2C-1), n ^C1 represents an integer of 1 or more. Preferably, it is an integer of 1 to 4, and particularly preferably 1 or 2.
Further, as a combination of n ^C1 and R ^CF1 , when n ^C1 = 1, R ^CF1 is a heptafluoro-n-propyl group or a nonafluoro-n-butyl group; when n ^C1 = 2, R ^CF1 is nonafluoro- More preferably, it is an n-butyl group.

In the general formula (2C-1), Y ^C11 and Y ^C12 is a hydrogen atom while the other represents SO ₃ M ^C, M ^C represents a cation. Examples of the cation represented by M ^C, for example, an alkali metal ion (lithium ion, sodium ion, potassium ion), alkaline earth metal ions (barium ion, calcium ion, etc.), an ammonium ion and the like are preferably exemplified The Of these, lithium ions, sodium ions, potassium ions or ammonium ions are particularly preferred, and sodium ions are most preferred.

  Specific examples of the compound represented by the general formula (2C) are shown below, but the compound represented by the general formula (2C) that can be used in the present invention is not limited by the following specific examples. Absent.

The compound represented by the general formula (2C) can be easily synthesized by using a general maleic anhydride or the like as a raw material and sequentially performing a monoesterification reaction, an acid halogenation, an esterification reaction, and a sulfonation reaction. is there. The counter cation can be easily converted with an ion exchange resin.
For specific synthesis methods, Synthesis Examples 6 to 9 described later can be referred to.

Next, the general formula (2D) will be described in detail.
General formula (2D)
[Rf ^D- (L ^D ) _nD ] _mD -W
In the formula, Rf ^D represents a perfluoroalkyl group, L ^D represents an alkylene group, and W has an anionic group, a cationic group, a betaine group, or a nonionic polar group necessary for imparting surface activity. Represents a group. n ^D represents an integer of 0 or 1, m ^D represents an integer of 1-3.

Rf ^D represents a C 3-20 perfluoroalkyl group, and specific examples thereof include C ₃ F ₇ -group, C ₄ F ₉ -group, C ₆ F ₁₃ -group, C ₈ H ₁₇ -group, C _{8 And 12} F ₂₅ -group, C ₁₆ F ₃₃ -group, and the like.

The L ^D group represents an alkylene group. The alkylene group has 1 or more carbon atoms, preferably 2 or more, and preferably 20 or less. Specifically, methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, 1,6-hexylene group, 1,2-octylene. Groups and the like.

In the silver halide photographic light-sensitive material of the present invention, a mixture of a plurality of compounds in which Rf ^D is a perfluoroalkyl group having a chain length different from each other may be used, or only a compound having a single perfluoroalkyl group. It may be used. A mixture of a plurality of compounds having the same Rf ^{D and} different L ^D may be used.
In the present invention, when a mixture of a plurality of compounds in which Rf ^D is a perfluoroalkyl group having a chain length different from each other is used, the average value of the chain length of the perfluoroalkyl group is preferably 4 to 10 carbon atoms. 4 to 9 is particularly preferable.

n ^D represents an integer of 0 or 1, and is preferably 1. m ^D represents an integer of 1 to 3, and when m ^D is 2 or 3, [Rf ^D- (L ^D ) n ^D ] may be the same as or different from each other. When W is not a phosphate ester group, m ^D = 1 is preferable. When W represents a phosphate ester group, any of m ^D = 1 to 3 may be used, and when m ^D = 1 to 3 is a mixture, The average value is preferably 0.5-2.

  W represents a group having a cationic group, an anionic group, a betaine group, or a polar nonionic group necessary for imparting surface activity. As long as these groups are included, the connection method with Rc is not limited. Examples of anionic groups necessary for imparting surface activity include sulfonic acid groups and their ammonium or metal salts, carboxylic acid groups and their ammonium or metal salts, phosphonic acid groups and their ammonium or metal salts, sulfate ester groups and Examples thereof include ammonium or metal salts thereof, phosphate ester groups and ammonium or metal salts thereof.

Examples of cationic groups necessary for imparting surface activity include quaternary alkylammonium groups such as trimethylammoniumethyl group and trimethylammoniumpropyl group; aromatic ammonium such as dimethylphenylammoniumalkyl group and N-methylpyridinium group Groups. An appropriate counter ion exists in these groups, and examples thereof include a halogen atom, a benzenesulfonate anion, a toluenesulfonate anion, and the like, and a toluenesulfonate anion is preferable.
Examples of the betaine group necessary for imparting surface activity include groups having a betaine structure such as —N ⁺ (CH ₃ ) ₂ CH ₂ COO ⁻ and —N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ COO ^— Is mentioned.
Examples of nonionic groups necessary for imparting surface activity include polyoxyalkylene groups and polyhydric alcohol groups, with polyoxyalkylene groups such as polyethylene glycol and polypropylene glycol being preferred. However, the terminal of these groups may be a group other than a hydrogen atom, for example, an alkyl group.

In the general formula (2D), Rf ^D is preferably a perfluoroalkyl group having 4 to 16 carbon atoms, and more preferably a perfluoroalkyl group having 6 to 16 carbon atoms. L ^D preferably represents an alkylene group having 2 to 16 carbon atoms, more preferably represents an alkylene group having 2 to 8 carbon atoms, and particularly preferably represents an ethylene group. n ^D is preferably 1.
L ^D and the group necessary for imparting surface activity may be bonded in any manner, for example, they can be bonded by an alkylene chain, arylene, etc., and these groups may have a substituent. . These groups may contain an oxy group, a thio group, a sulfonyl group, a sulfoxide group, a sulfonamide group, an amide group, an amino group or the like in the main chain or side chain.

  Specific examples of the compound represented by the general formula (2D) are shown below, but the compound represented by the general formula (2D) that can be used in the present invention is not limited by the following specific examples. Absent.

  The compound represented by the above general formula (2D) can be produced by a usual synthesis method, and those widely marketed as so-called telomer type perfluoroalkyl group-containing surfactants can be used. . Examples include ZONYL FSP, FSE, FSJ, NF, TBS, FS-62, FSA, FSK (more ionic), ZONYL 9075, FSO, FSN, FSN-100, FS-300, manufactured by DUPONT Corporation. FS-310 (more non-ionic), S-111, S-112, S-113, S-121, S-131, S-132 (more ionic), S-141, S manufactured by Asahi Glass Co., Ltd. -145 (more nonionic), Unidyne DS-101, DS-102, DS-202, DS-301 (more ionic), DS-401, DS-403 (more nonionic) manufactured by Daikin Industries, Ltd. And the like.

  Of the various compounds described above, ionic surfactants are used in various different salt forms by means of ion exchange or neutralization, etc., depending on the purpose of use, various properties required, etc. It can be used in the presence of two or more counter ions.

Hereinafter, examples of the substituent which the substitutable group in the above general formula may have and the substituent T will be described.
Examples of the substituent T include an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms. Examples thereof include a methyl group, an ethyl group, and isopropyl. Group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like, alkenyl group (preferably having 2 to 20 carbon atoms, more preferably). Is an alkenyl group having 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group, and an alkynyl group (preferably a carbon atom). An alkynyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as a propargyl group, 3 A pentynyl group), an aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as a phenyl group and p-methyl group). A phenyl group, a naphthyl group, etc.), a substituted or unsubstituted amino group (preferably a carbon number of 0-20, more preferably a carbon number of 0-10, particularly preferably a carbon number of 0-6, For example, an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, etc.)

An alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group). An aryloxy group (preferably an aryloxy group having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyloxy group and a 2-naphthyloxy group. An acyl group (preferably having a carbon number of 1-20, more preferably a carbon number of 1-16, particularly preferably a carbon number of 1-12, such as an acetyl group, a benzoyl group, a formyl group, a pivaloyl group, etc. An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 2 carbon atoms). 2 alkoxycarbonyl groups, for example, methoxycarbonyl group, ethoxycarbonyl group and the like, and aryloxycarbonyl groups (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably carbon numbers). An aryloxycarbonyl group having 7 to 10 carbon atoms, such as a phenyloxycarbonyl group, an acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 2 carbon atoms). 10 acyloxy groups such as an acetoxy group and a benzoyloxy group)

An acylamino group (preferably an acylamino group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as an acetylamino group and a benzoylamino group), alkoxycarbonyl An amino group (preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group), aryloxy Carbonylamino group (preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as a phenyloxycarbonylamino group) Sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferred Or a sulfonylamino group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfonylamino group and a benzenesulfonylamino group, and a sulfamoyl group (preferably having a carbon number of 0 to 20). More preferably, it is a sulfamoyl group having 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, and examples thereof include a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, and a phenylsulfamoyl group. ), A carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, an unsubstituted carbamoyl group, a methylcarbamoyl group, diethylcarbamoyl group Group, phenylcarbamoyl group, etc.),

An alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, more preferably an alkylthio group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a methylthio group and an ethylthio group), an arylthio group ( Preferably it is C6-C20, More preferably, it is C6-C16, Most preferably, it is C6-C12 arylthio group, for example, a phenylthio group etc. are mentioned, A sulfonyl group (preferably C1-C1). 20, more preferably a sulfonyl group having 1 to 16 carbon atoms, particularly preferably a sulfonyl group having 1 to 12 carbon atoms, such as a mesyl group and a tosyl group, and a sulfinyl group (preferably having a carbon number of 1 to 20, more A sulfinyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms is preferable. Zensulfinyl group and the like), ureido group (preferably a ureido group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, an unsubstituted ureido group , Methylureido group, phenylureido group, etc.),

Phosphoric acid amide group (preferably a phosphoric acid amide group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide group, phenylphosphoric acid amide Group), hydroxy group, mercapto group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino Group, imino group, heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, for example, a heterocyclic group having a hetero atom such as nitrogen atom, oxygen atom, sulfur atom, etc. For example, imidazolyl group, pyridyl group, quinolyl group, furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzii A dazolyl group, a benzthiazolyl group, and the like), a silyl group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms. Group, triphenylsilyl group, etc.). These substituents may be further substituted. Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be bonded to each other to form a ring.

Next, the silver halide emulsion used for the silver halide photographic light-sensitive material of the present invention will be described.
The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is silver bromide, silver chloride, silver iodide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloroiodobromide, Any of silver iodochloride and the like is preferably used. The form of the silver halide grains may be normal crystals such as octahedrons, cubes, and tetradecahedrons, but tabular grains are more preferred.

The following examples can be given as preferred tabular grains.
(1) A tabular grain having a (111) plane as a main surface and two parallel twin planes, the grain fringe portion containing 10 or more dislocation lines per grain, and a silver chloride content of 10 Tabular silver halide grains having an aspect ratio of 2 or more, comprising less than mol% of silver iodobromide or silver chloroiodobromide,
(2) A tabular grain having a (111) plane as a main surface and two parallel twin planes, and at least one per grain per grain apex and / or side and / or main plane A tabular silver halide grain having an aspect ratio of 2 or more, comprising silver iodobromide or silver chloroiodobromide having an epitaxial junction of
(3) A tabular silver halide comprising silver iodobromide or silver chloroiodobromide having a parallel main plane of (100) plane, an aspect ratio of 2 or more, and a silver chloride content of less than 10 mol% Silver halide grains,
(4) Tabular silver halide grains having a parallel principal plane of (111) plane or (100) plane and an aspect ratio of 2 or more and containing at least 80 mol% of silver chloride.

  Regarding the particles of (1), for example, JP-A-62-220238, JP-A-3-213845, JP-A-4-181939, JP-A-6-278745, JP-A-6-27564, and JP-A-11-298932. JP-A-2001-228572, JP-A-2002-268162, and the like describe in detail in the text of each gazette and are preferably used in the present invention.

  Regarding the particles of the above (2), for example, JP-A Nos. 2001-235821, 2002-169241, 2002-169239, 2002-278008, 2002-271717 and the like are described in detail in the text of each publication. And is preferably used in the present invention.

  The particles (3) and (4) are described in detail in the text of Japanese Patent Application Laid-Open No. 2002-122955, for example, and are preferably used in the present invention.

  In the present invention, any of the above-described tabular silver halide grains (1) to (4) is preferably used, but the grain (1) is more preferable.

  The following is a detailed description of the particles that are more preferably used in the present invention.

  In the present invention, an emulsion in which tabular grains (also referred to as tabular grains) having a (111) plane as the main surface and having two parallel twin planes account for 95 to 100% of the total grains in the grain number ratio is preferable. More preferably, the same particles occupy 97 to 100%.

  The twin plane means the (111) plane when ions at all lattice points are mirror images on both sides of the (111) plane. The tabular grains are triangular or hexagonal when the grains are viewed from the direction perpendicular to the main surface, or have rounded corners and sides. The shape has hexagonal parallel main surfaces.

  In the present invention, an emulsion in which hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1 to 1.5 occupy 50 to 100% of the total number of grains is preferable. More preferably, it occupies 70 to 100%, and more preferably 80 to 100%. Particularly preferably, hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1 to 1.2 occupy 50 to 100% of the total number of grains. More preferably 70 to 100%, particularly preferably 80 to 100%.

  In the present invention, the twin plane spacing of tabular grains is 0.012 μm or less as described in US Pat. No. 5,219,720, or (111) as described in JP-A-5-249585. The main surface distance / twin plane distance may be 15 or more, and may be selected according to the purpose.

  In the present invention, the average equivalent circular equivalent diameter of the tabular grains is preferably 0.5 μm to 5.0 μm, more preferably 0.6 μm to 4.0 μm, and still more preferably 0.7 μm to 3.5 μm.

  The equivalent circle equivalent diameter in the present invention is the diameter of a circle having an area equal to the projected area of the main surface of the particle. The average equivalent circular equivalent diameter is an arithmetic average of equivalent circular equivalent diameters of all tabular grains in the emulsion.

  The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification. The thickness of the particles can be easily calculated by depositing metal from the oblique direction of the particles together with the latex for reference, measuring the shadow length on an electron micrograph, and calculating with reference to the shadow length of the latex. Desired.

  In the present invention, the average grain thickness of the tabular grains is preferably 0.05 to 0.30 μm, more preferably 0.07 to 0.25 μm, and still more preferably 0.10 to 0.20 μm. The average grain thickness is the arithmetic average of the grain thicknesses of all tabular grains in the emulsion.

  The ratio of the equivalent circle equivalent diameter to the silver halide grain thickness is called the aspect ratio. That is, it is a value obtained by dividing the equivalent circle diameter of the projected area of each silver halide grain by the grain thickness. As an example of the aspect ratio measurement method, there is a method of obtaining a diameter (equivalent circle equivalent diameter) and thickness of a circle having an area equal to the projected area of each particle by taking a transmission electron micrograph by a replica method. In this case, the thickness is calculated from the length of the shadow of the replica.

  In this invention, it is preferable that the average aspect-ratio of a tabular grain is 2-50, More preferably, it is 8-40, More preferably, it is 12-40. The average aspect ratio is an arithmetic average of the aspect ratios of all tabular grains in the emulsion.

  In the present invention, it is preferable to use an emulsion composed of monodisperse grains. The variation coefficient of the grain size (equivalent sphere equivalent diameter) distribution of all the grains in the emulsion is preferably 3 to 35%, more preferably 3 to 20%, still more preferably 3 to 15%. The variation coefficient of the equivalent sphere equivalent diameter distribution is obtained by multiplying the value obtained by dividing the variation (standard deviation) of the equivalent sphere equivalent diameter of each tabular grain by the average equivalent sphere equivalent diameter by 100.

  In the present invention, the variation coefficient of the equivalent circle equivalent diameter distribution of all the grains in the emulsion is preferably 3 to 35%, more preferably 3 to 25%, still more preferably 3 to 15%. The variation coefficient of the equivalent circle equivalent diameter distribution is obtained by multiplying the value obtained by dividing the variation (standard deviation) of the equivalent circle equivalent diameter of each particle by the average equivalent circle equivalent diameter by 100.

  In the present invention, the variation coefficient of the grain thickness distribution of all tabular grains in the emulsion is preferably 3 to 25%, more preferably 3 to 20%, and further preferably 3 to 15%. The variation coefficient of the grain thickness distribution is obtained by multiplying the value obtained by dividing the grain thickness variation (standard deviation) of each tabular grain by the average grain thickness by 100.

  In the present invention, the variation coefficient of the twin plane spacing distribution of all tabular grains in the emulsion is preferably 3 to 25%, more preferably 3 to 20%, still more preferably 3 to 15%. The variation coefficient of the twin plane spacing distribution is a value obtained by dividing the thickness variation (standard deviation) of the twin plane spacing of each tabular grain by the average twin plane spacing.

  In the present invention, the grain thickness, aspect ratio, and monodispersity in the above range may be selected according to the purpose, but it is preferable to use tabular grains having a thin grain thickness and a high aspect ratio and monodisperse.

  In the present invention, various methods can be used as a method for forming high aspect ratio tabular grains. For example, the grain formation described in US Pat. Nos. 5,496,694 and 5,498,516 is described. Can be used.

  In order to form monodispersed and high aspect ratio tabular grains, it is important to form small twin nuclei within a short time. Therefore, it is preferable to perform nucleation in a short time under low temperature, high pBr, low pH, and low gelatin content. As the types of gelatin, low molecular weight, low methionine content, amino groups can be converted to phthalic acid or triglyceride. Those modified with merit acid or pyromellitic acid are preferred.

After nucleation, normal ripening, single twin and non-parallel multiple twin nuclei disappear by physical ripening, and selectively leave parallel double twin nuclei. Further aging between the remaining parallel double twin nuclei is preferable because of increasing monodispersity.
It is also preferable to perform physical ripening in the presence of PAO (polyalkylene oxide) described in, for example, US Pat. No. 5,147,771 to increase monodispersity.

  Then, after adding gelatin, soluble silver salt and soluble halogen salt are added, and grain growth is performed. As the additional gelatin, those having an amino group modified with phthalic acid, trimellitic acid or pyromellitic acid are preferable.

It is also preferable to grow silver grains by supplying silver and halides by adding silver halide fine grains prepared separately in advance or simultaneously in another reaction vessel.
Even during grain growth, it is important to control and optimize the temperature, pH, binder amount, pBr, silver and halogen ion supply rates of the reaction solution.

In order to form silver halide emulsion grains that are more preferable in the present invention, silver iodobromide or silver chloroiodobromide is used. In the case of having a phase containing iodide or chloride, these phases may be uniformly distributed or localized in the grains.
Other silver salts such as rhodium silver, silver sulfide, silver selenide, silver carbonate, silver phosphate and organic acid silver may be contained as separate grains or as part of silver halide grains.

In the present invention, the range of the silver bromide content of the emulsion grains is preferably 80 mol% or more, more preferably 90 mol% or more.
Moreover, the range of preferable silver iodide content is 1-20 mol%, More preferably, it is 2-15 mol%, More preferably, it is 3-10 mol%.

  In the present invention, the variation coefficient of the silver iodide content distribution between the grains of the emulsion grains is preferably 30% or less, more preferably 3 to 25%, and particularly preferably 3 to 20%. The variation coefficient of the silver iodide content distribution between grains is obtained by multiplying the value obtained by dividing the standard deviation of the silver iodide content of each emulsion grain by the average silver iodide content by 100. The silver iodide content of individual emulsion grains can be measured by analyzing the composition of each grain using an X-ray microanalyzer.

  The measuring method is described in European Patent No. 147,868, for example. When determining the distribution of silver iodide content of individual grains of the emulsion, it is preferable to determine by measuring the silver iodide content of at least 100 grains, more preferably 200 grains or more, particularly preferably 300 grains or more. Measure for and find out.

  In the present invention, the surface iodine content of the emulsion is preferably 5 mol% or less, more preferably 4 mol% or less, and still more preferably 3 mol% or less. The measurement of the surface iodine content can be confirmed by the ESCA (also called XPS) method (a method in which photoelectrons emitted from the particle surface are irradiated with X-rays).

  In the present invention, emulsion grains mainly composed of (111) planes and (100) planes are preferred, and the ratio of (111) planes to the entire surface of the emulsion grains is preferably at least 70%.

  In the present invention, grains in which (100) faces appear on the side surfaces of the tabular grains are preferred, and the ratio of the area where (100) faces occupy the emulsion grain surfaces to the area where (111) faces occupy the emulsion grain surfaces is at least It is preferably 2%, more preferably 4% or more. For controlling the (100) surface ratio, reference can be made to JP-A-2-298935 and JP-A-8-334850. The (100) face ratio is determined by a method using the difference in adsorption dependency between the (111) face and the (100) face in the adsorption of the sensitizing dye, for example, T. Tani, J. Imaging Sci., 29, 165 (1985 ) And the like.

  In the present invention, the area ratio of the (100) plane on the side surface of the tabular grain is preferably 15% or more, more preferably 25% or more. The area ratio of the (100) plane on the side surface of the tabular grain can be determined, for example, from the method described in JP-A-8-334850.

In the present invention, tabular grains having dislocation lines inside the grains are preferably used.
The introduction of dislocation lines into the tabular grains will be described below.
A dislocation line is a linear lattice defect at the boundary between a region that has already slipped and a region that has not yet slipped on the slip plane of the crystal. Regarding dislocation lines of silver halide crystals, 1) CRBerry, J. Appl. Phys., 27,636 (1956), 2) CRBerry, DCSkilman, J. Appl. Phys., 35, 2165 (1964), 3) JF Hamilton, Phot.Sci.Eng., 11, 57 (1967), 4) T. Shiozawa, J. Soc. Phot. Sci. Jap., 34, 16 (1971), 5) T. Shiozawa, J. Soc. There are documents such as Sci. Jap., 35, 213 (1972), which can be analyzed by an X-ray diffraction method or a direct observation method using a low-temperature transmission electron microscope. When observing dislocation lines directly using a transmission electron microscope, the silver halide grains taken out from the emulsion are placed on a mesh for electron microscope observation, taking care not to apply such a pressure that the dislocation lines are generated on the grains. Observation is performed by the transmission method in a state where the sample is cooled so as to prevent damage (for example, printout) by the electron beam.

  In this case, since the electron beam is less likely to be transmitted as the particle thickness is thicker, it is possible to observe more clearly by using an electron microscope of a high pressure type (200 kV or more with respect to a thickness of 0.25 μm).

  On the other hand, there is a literature of GCFarnell, RBFlint, JBChanter, J.Phot.Sci., 13, 25 (1965) as an effect of dislocation lines on photographic performance. In silver particles, it is shown that the location where latent image nuclei are formed and defects in the particles are closely related. For example, U.S. Pat. Nos. 4,806,461, 5,498,516, 5,496,694, 5,476,760, 5,567,580, JP-A-4-149541 No. 4-149737 discloses a technique for controlling the introduction of dislocation lines into silver halide grains. In these patents, it has been shown that tabular grains having dislocation lines are superior in photographic characteristics such as sensitivity and pressure properties compared to tabular grains having no dislocation lines.

  In the present invention, dislocation lines are preferably introduced into the tabular grains as follows. That is, dislocation lines are introduced by epitaxial growth of a silver halide phase containing silver iodide on a base tabular grain (also referred to as host grain) and subsequent formation of a silver halide shell.

The method for introducing dislocation lines into the tabular grains of the present invention will be described in detail.
First, the silver iodide content of the host grain is 0 to 10 mol%, more preferably 0 to 5 mol%, and still more preferably 0 to 3 mol%.

  Next, silver halide epitaxy containing silver iodide is formed on the host grains. In the present invention, the silver halide epitaxy containing silver iodide is formed on either the upper side or the lower side of the host tabular grain fringe portion. The host tabular grain fringe portion refers to a grain peripheral region on the inner side by a length corresponding to the grain thickness from the outer periphery of the grain side surface as seen from the direction perpendicular to the grain main surface.

  The composition of the silver halide phase to be epitaxially grown on the host grain preferably has a higher silver iodide content. The silver halide phase to be epitaxially grown may be any of silver iodide, silver iodobromide, silver chloroiodobromide and silver chloroiodide, but is preferably silver iodide or silver iodobromide. More preferably. The preferred silver iodide (iodide ion) content in the case of silver iodobromide is 1 to 45 mol%, more preferably 5 to 45 mol%, based on the amount of silver in the silver halide phase to be epitaxially grown. Particularly preferred is 10 to 45 mol%. The higher the silver iodide content, the better in terms of forming misfit necessary for introducing dislocation lines, but 45 mol% is the solid solubility limit of silver iodobromide.

  The amount of silver iodide or iodide ion added to form this high silver iodide content phase to be epitaxially grown on the host grain is preferably 2 to 10 mol% of the silver amount of the host grain. Preferably it is 2-8 mol%, Most preferably, it is 2-6 mol%. If it is less than 2 mol%, dislocation lines are hardly introduced, and if it exceeds 10 mol%, the development speed is delayed, such being undesirable.

  At this time, the high silver iodide content phase is preferably present in the range of 10 to 60 mol%, more preferably in the range of 20 to 40 mol% of the total grain silver amount after the grain formation. Is to exist. Even if it is less than 10 mol% or exceeds 60 mol%, it is difficult to obtain high sensitization by introduction of dislocation lines, which is not preferable.

In the present invention, when the high silver iodide content phase is formed on the host grain, for example, Japanese Patent Publication No. 7-111549, Japanese Patent Application Laid-Open Nos. 5-341418, 5-346663, 5-323487, and 6 -11780, 6-111781, 6-111782, 6-111784, 6-27574, 6-138595, 6-230495, 6-242527, 6-2250309 6-250310, 6-250311, 6-250313, 6-258745, 6-273766, 6-313933, 7-219102, 8-62754, 8 -95181, US Pat. Nos. 5,389,508, 5,418,124, 5,482,826, 5,496,694, 5,498,51 No. 5,580,713 and 5,527,664, etc., and the method of releasing iodide ions from an iodide ion releasing agent by reaction with an alkali or a nucleophile. preferable. That is, it is an iodide ion releasing agent represented by the following formula (A). The method described in the said patent application can be preferably used for the usage.
Formula (A)
R-I

  In the formula (A), R represents a monovalent organic residue that releases an iodine atom in the form of an iodide ion by reaction with a base and / or a nucleophile. The compound represented by the formula (A) will be described in more detail. R is, for example, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 3 carbon atoms, or the number of carbon atoms. C3-C30 cycloalkyl group, C6-C30 aryl group, C7-C30 aralkyl group, C4-C30 heterocyclic group, C1-C30 acyl group, C1-C30 Carbamoyl group, alkyl having 2 to 30 carbon atoms or aryloxycarbonyl group having 7 to 30 carbon atoms, alkyl having 1 to 30 carbon atoms, arylsulfonyl group having 6 to 30 carbon atoms, and sulfamoyl group are preferable. R is preferably the above group having 20 or less carbon atoms, and particularly preferably the above group having 12 or less carbon atoms. The carbon number is preferably within the above range in terms of solubility and addition amount.

  R is preferably substituted, and preferred substituents include the following. The substituent may be further substituted with another substituent. For example, halogen atoms (eg, fluorine, chlorine, bromine, iodine), alkyl groups (eg, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, cyclopentyl, cyclohexyl), alkenyl groups (eg, allyl) , 2-butenyl, 3-pentenyl), alkynyl groups (eg, propargyl, 3-pentynyl), aralkyl groups (eg, benzyl, phenethyl), aryl groups (eg, phenyl, naphthyl, 4-methylphenyl), heterocyclic groups ( For example, pyridyl, furyl, imidazolyl, piperidyl, morpholyl), alkoxy group (for example, methoxy, ethoxy, butoxy), aryloxy group (for example, phenoxy, naphthoxy), amino group (for example, unsubstituted amino, dimethylamino, ethylamino) Anilino), Acylua Group (for example, acetylamino, benzoylamino), ureido group (for example, unsubstituted ureido, N-methylureido, N-phenylureido), urethane group (for example, methoxycarbonylamino, phenoxycarbonylamino), sulfonylamino group ( For example, methylsulfonylamino, phenylsulfonylamino), sulfamoyl group (for example, sulfamoyl, N-methylsulfamoyl, N-phenylsulfamoyl), carbamoyl group (for example, carbamoyl, diethylcarbamoyl, phenylcarbamoyl), sulfonyl group ( For example, methylsulfonyl, benzenesulfonyl), sulfinyl group (eg, methylsulfinyl, phenylsulfinyl), alkyloxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl) Bonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, benzoyl, formyl, pivaloyl), acyloxy group (for example, acetoxy, benzoyloxy), phosphoric acid amide group (for example, N, N-diethyl) Phosphoric acid amide), alkylthio group (for example, methylthio, ethylthio), arylthio group (for example, phenylthio group), cyano group, sulfo group (including salts thereof), carboxyl group, hydroxy group, phosphono group, and nitro group.

  More preferred substituents for R are a halogen atom, an alkyl group, an aryl group, a 5- or 6-membered heterocyclic group containing at least one O, N or S, an alkoxy group, an aryloxy group, an acylamino group, a sulfamoyl group, A carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryloxycarbonyl group, an acyl group, a sulfo group (including salts thereof), a carboxyl group, a hydroxy group, and a nitro group. Particularly preferred substituents for R are a hydroxy group, a carbamoyl group, a lower alkylsulfonyl group or a sulfo group (including salts thereof) when substituting for an alkylene group in R, and when substituting for a phenylene group in R A sulfo group (including salts thereof).

  The iodide ion releasing agent of formula (A) releases iodide ions by reaction with an iodide ion release regulator (base and / or nucleophile). The nucleophile used in this case is preferably Chemical species. For example, hydroxide ion, sulfite ion, hydroxylamine, thiosulfate ion, metabisulfite ion, hydroxamic acids, oximes, dihydroxybenzenes, mercaptans, sulfinate, carboxylate, ammonia, amines, Examples include alcohols, ureas, thioureas, phenols, hydrazines, hydrazides, semicarbazides, phosphines, and sulfides. In the present invention, the release rate and timing of iodide ions can be controlled by controlling the concentration of the base or nucleophile, the addition method, and the temperature of the reaction solution. The base is preferably an alkali hydroxide.

The preferred concentration range of the iodide ion releasing agent and the iodide ion release controlling agent used for generating iodide ions is 1 × 10 ^{−7 to} 20M, more preferably 1 × 10 ^{−5 to} 10M, and still more preferably. It is 1 × 10 ^{−4 to} 5M, particularly preferably 1 × 10 ^{−3 to} 2M. When the concentration exceeds 20M, the amount of the iodide ion release agent and iodide ion release regulator having a large molecular weight is excessively increased with respect to the capacity of the particle formation container, which is not preferable. On the other hand, if it is less than 1 × 10 ⁻⁷ M, the iodide ion releasing reaction rate becomes too slow, such being undesirable.

  In the present invention, when a base is used in releasing iodide ions, a change in solution pH may be used. At this time, a preferable pH range for controlling the release rate and timing of iodide ions is 2 to 12, more preferably 3 to 11, particularly preferably 5 to 10, and most preferably adjusted pH is 7. The range is from 5 to 10.0. Even under neutral conditions at pH 7, hydroxide ions determined by the ionic product of water act as regulators. Further, a nucleophile and a base may be used in combination, and at this time, the pH may be controlled within the above range to control the release rate and timing of iodide ions. When iodine atoms are released from the iodide ion releasing agent in the form of iodide ions, all iodine atoms may be released or a part of them may remain without being decomposed.

Regarding the above-mentioned iodide ion releasing agent, it is preferable to use the specific compounds and the usage thereof described in the aforementioned patent application.
After the high silver iodide content phase is epitaxially grown on the host grain, dislocation lines are introduced when a silver halide shell is formed outside the host tabular grain. The silver halide shell may be composed of silver bromide, silver iodobromide, or silver chloroiodobromide, but is preferably silver bromide.

  The amount of silver used for the silver halide shell growth is preferably 10 to 60 mol%, more preferably 20 to 40 mol%, based on the total amount of grain silver.

  The preferable temperature in the above-mentioned dislocation line introduction process is 30 to 75 ° C., more preferably 30 to 60 ° C., and further preferably 30 to 50 ° C. in the above dislocation line introduction process. Moreover, various values can be selected for pAg in the range of 7 to 11 in the above-described dislocation line introduction process.

Further, at a certain time of the above-described dislocation line introduction process, for example, in the present application, a spectral sensitizing dye or Research Disclosure Item 17643 (December 1978), Item 18716 (November 1979) and Item 308119 are disclosed. (December 1989) adsorbs a substance such as a mercapto compound described as an antifoggant on the particle surface, such as a mercapto compound described in JP-A-3-39946 or a crystal phase control agent described in JP-A-8-220664. It is preferable to prevent dissolution of particles. These substances can be freely selected as long as they are adsorbed on the particle surface to prevent dissolution of the particles and do not impair photographic performance. The surface selectivity when these substances are adsorbed on the surface of the silver halide may be selected from, for example, the (111), (100), (110) faces, or combinations thereof. What moderately prevents the dissolution of the particle side surface is preferable.
The preferred addition amount of these substances is generally in the range of 1 × 10 ⁻⁴ to 5 × 10 ⁻³ mole per mole of silver halide. The addition time can be selected before, during or after the epitaxial growth, or during the formation of the silver halide shell, but is preferably added after the epitaxial growth, that is, before the formation of the silver halide shell.

  The dislocation line introduction position and density of tabular grains will be described below. In the case of tabular grains, the position and number of dislocation lines for each grain when viewed from a direction perpendicular to the main surface can be obtained from a photograph of the grain taken using an electron microscope as described above. When introducing dislocation lines into tabular grains, it is preferable to limit the grain fringes as much as possible.

  In the present invention, many emulsions containing tabular grains having 10 or more dislocation lines in the grain fringe part are preferred, and emulsions containing many tabular grains having 30 or more dislocation lines in the grain fringe part are preferred. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, the number is roughly 10, 20, or 30.

  In the present invention, the tabular grains preferably have a uniform dislocation dose distribution between grains from the viewpoint of homogeneity between grains. In the emulsion used in the present invention, tabular grains containing 10 or more dislocation lines per grain in the grain fringe part preferably occupy 50% or more, more preferably 80% or more of the total grains. In the present invention, tabular grains containing 30 or more dislocation lines per grain in the grain fringe part further occupy 50% or more, more preferably 8% or more.

  Further, it is desirable that the tabular grains of the emulsion have uniform dislocation line introduction positions in the grains. In the emulsion used in the present invention, the silver halide tabular grains in which dislocation lines are localized substantially only in the grain fringe portion preferably occupy 50% or more of the total grains, more preferably 60% or more, Preferably it occupies 80% or more.

  “Substantially only the particle fringe part” means that five or more dislocation lines are not included in the particle fringe part, that is, the particle center part. The particle central portion refers to an inner region surrounded by a fringe region when the particle is viewed from a direction perpendicular to the main surface.

  Further, the tabular grains of the emulsion used in the present invention preferably have dislocation lines over many fringe regions, and the tabular grains having dislocation lines in the fringe portions over 50% or more of the grain fringe regions. It is preferable to occupy 50% or more of the total number of particles, more preferably 60% or more, and still more preferably 80% or more. Further, it is also preferred that tabular grains having dislocation lines in the fringe portion over 70% or more of the grain fringe region occupy 50% or more of the total grains, more preferably 60% or more, and still more preferably 80%. Occupy more than 50%.

Further, when the length of each dislocation line can be clearly counted, it is also preferable in the present invention that the length of the dislocation line in the tabular grain is uniform.
When determining the ratio of dislocation lines and the number of dislocation lines in the present invention, it is preferable to directly observe the dislocation lines for at least 100 particles, more preferably 200 particles or more, particularly preferably 300 particles or more. Observe by observing.

  Further, in the present invention, 50% or more (grain number ratio) of the total grains in the emulsion has an average silver iodide content of 2 mol% or more than the average silver iodide content in the center of the grain fringe. It is also preferably occupied by high tabular grains, more preferably the average silver iodide content of the grain fringe part is 4 mol% or more, more preferably the grain fringe part of the grain fringe part. The average silver iodide content is occupied by tabular grains that are at least 5 mol% higher than the average silver iodide content at the center of the grain. The particle center is a region inside the particle fringe.

  The silver iodide content in the tabular grains can be determined by the method described in JP-A-7-219102 using, for example, an analytical electron microscope.

  In the present invention, the tabular grains preferably contain one or more kinds of photographically useful metal ions or complexes (hereinafter referred to as “metal (complex) ions”).

The metal ion doping into the silver halide grains will be described below.
Photographically useful metal (complex) ions are those doped in the grains for the purpose of improving the photographic properties of the photosensitive silver halide emulsion. These compounds act as a transient or permanent trap of electrons or holes in the silver halide crystal, and can provide effects such as high sensitivity, high contrast, reciprocity characteristics improvement, and pressure improvement.

  In the present invention, first to third transition metal elements such as iron, ruthenium, rhodium, palladium, cadmium, rhenium, osmium, iridium, platinum, chromium and vanadium, and amphoteric metal elements such as gallium, indium, taum and lead are emulsions. The metal doped in the particles is preferable. These metal ions are doped in the form of complex salts or single salts. In the case of complex ions, hexacoordinate halogeno complexes and cyano complexes having halogen ions or cyan (CN) ions as ligands are preferably used.

Also, nitrosyl (NO) ligand, thionitrosyl (NS) ligand, carbonyl (CO) ligand, thiocarbonyl (NCO) ligand, thiocyan (NCS) ligand, selenocyanate (NCSe) ligand, tellurocyanate (CNTe) ligand, dynite Complexes having organic ligands such as rhogen (N ₂ ) ligands, azide (N ₃ ) ligands, bipyridyl ligands, cyclopentadienyl ligands, 1,2-dithiorenyl ligands, imidazole ligands, etc. Can be used. The following multidentate ligands may be used as the ligand. That is, any of bidentate ligands such as bipyridyl ligands, tridentate ligands such as diethylenetriamine, tetradentate ligands such as triethylenetetraamine, and hexadentate ligands such as ethylenediaminetetraacetic acid. It may be used. The number of ligands is preferably 6, but may be 4. As the organic ligand ligand, those described in US Pat. Nos. 5,457,021, 5,360,712 and 5,462,849 are preferably used. Furthermore, it is also preferable to incorporate metal ions as oligomers.

  When incorporating metal (complex) ions into silver halide, it is important that the size of the metal (complex) ions is compatible with the silver halide interstitial distance. In addition, it is essential for the silver halide to be doped that a compound of metal (complex) ions with silver or halogen ions coprecipitates with silver halide. Therefore, the pKsp (the common logarithm of the reciprocal of the solubility product) of the compound of the metal (complex) ion with silver or halogen ion is about the same as the pKsp of silver halide (silver chloride 9.8, silver bromide 12.3, silver iodide 16.1) Need to be. Accordingly, the pKsp of the compound of metal (complex) ion with silver or halogen ion is preferably 8-20.

The amount of the metal complex doped into the silver halide grains is generally in the range of 10 ⁻⁹ to 10 ⁻² mol per mol of silver halide. Specifically, metal complexes that provide transient shallow electron traps in the light-sensitive process range from 10 ^-6 to 10 ^-2 moles per mole of silver halide, and metal complexes that provide deep electron traps in the light-sensitive process are silver halides. It is preferably used in the range of 10 ⁻⁹ to 10 ⁻⁵ mol per mol.

  The metal (complex) ion content of the emulsion grains can be confirmed by atomic absorption, polarized Zeeman spectroscopy, and ICP analysis. The ligand of the metal complex ion can be confirmed by infrared absorption (particularly FT-IR).

  The above-described doping of the metal (complex) ions into the silver halide grains may be carried out by using the surface phase or internal phase of the grains or metal ions as described in US Pat. Nos. 5,132,203 and 4,997,751. Any of the extremely shallow surface phases (so-called subsurfaces) that do not expose the surface to the surface may be selected according to the purpose. A plurality of metal ions may be doped, and they may be doped in the same phase or in different phases. As a method for adding these compounds, the metal salt solution may be mixed and added to an aqueous halide solution or a water-soluble silver salt solution at the time of grain formation, or the metal salt solution may be added directly. Further, silver halide emulsion fine grains doped with the metal ions may be added. When the metal salt is dissolved in water or an appropriate solvent such as methanol or acetone, an aqueous hydrogen halide solution (eg, HCl, HBr), thiocyanic acid or a salt thereof, or an alkali halide (eg, KCl) is used to stabilize the solution. , NaCl, KBr, NaBr, etc.) is preferably used. Moreover, it is also preferable from the same point to add an acid, an alkali, etc. as needed.

  When the emulsion is doped with metal ions of a cyano complex, cyan may be generated by the reaction of gelatin and the cyano complex to inhibit gold sensitization. In such a case, for example, as described in JP-A-6-308653, it is preferable to use a compound having a function of inhibiting the reaction between gelatin and a cyano complex. Specifically, it is preferable to perform the steps after doping the metal ion of the cyano complex in the presence of a metal ion that coordinates with gelatin such as zinc ion.

  The following is a general description of the emulsion used in the present invention. The photographic emulsions used in the present invention are "Photophysics and Chemistry" by Grafkide, published by Paul Monter (P.Glafkides, Chemiet Phisique Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press. (GFDuffin, Photographic Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photoemulsions" by Zerikman et al., Published by Focal Press (VLZelikman et al., Making and Coating Photographic Emulsion, Focal Press, 1964), etc. It can be prepared using the method described in 1. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used as a form for reacting a soluble silver salt and a soluble halogen salt. Good. A method (so-called back mixing method) in which grains are formed in the presence of excess silver ions can also be used. As one type of the simultaneous mixing method, a method of keeping pAg in a liquid phase generated by silver halide constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

  US Pat. Nos. 4,334,012, 4,301,241, and 4,150,994, and a method of adding silver halide grains precipitated in advance to a reaction vessel for preparing an emulsion. The method described in is sometimes preferred. These can be used as seed crystals or are effective when supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size. As the addition method, the whole amount can be added at once, divided into a plurality of times, or added continuously, or the like. It is also effective in some cases to add grains having various halogen compositions in order to modify the surface.

  US Pat. Nos. 3,477,852, 4,142,900, European Patents 273,429, and US Pat. Nos. 3,477,852 are used to convert most or only a small part of the halogen composition of silver halide grains. No. 273,430, West German Patent No. 3,819,241 and the like, which are effective particle forming methods. A soluble halogen solution or silver halide grains can be added to convert to a more sparingly soluble silver salt. You can choose from methods that convert at once, convert multiple times, or convert continuously.

  As a method for grain growth, in addition to the method of adding soluble silver salt and halogen salt at a constant concentration and a constant flow rate, British Patent No. 1,469,480, US Pat. Nos. 3,650,757 and 4,242 are used. No. 445, the particle forming method in which the concentration is changed or the flow rate is changed is a preferable method. By increasing the concentration or increasing the flow rate, the supplied silver halide amount can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of supplied silver halide if necessary. In addition, when a plurality of soluble silver salts with different solution compositions are added, or when a plurality of soluble halogen salts with different solution compositions are added, an addition method of increasing one and reducing the other is also an effective method. It is.

  A mixer for reacting a soluble silver salt solution with a soluble halogen salt is disclosed in U.S. Pat. Nos. 2,996,287, 3,342,605, 3,415,650, and 3,785. 777, West German Patent No. 2,556,885, and No. 2,555,364.

  Silver halide solvents are useful for the purpose of promoting ripening. For example, it is known to have an excess of halogen ions in the reactor to promote aging. Other ripening agents can also be used. These ripening agents can be mixed in the total amount in the dispersion medium in the reactor before adding silver and halide salts, and in addition to the addition of halide salts, silver salts or peptizers, Can also be introduced. As another variant, the ripening agent can be introduced independently at the halide and silver salt addition stage.

  As the ripening agent, for example, ammonia, thiocyanate (for example, rodankari, rhodammonium), organic thioether compound (for example, U.S. Pat. Nos. 3,574,628, 3,021,215, 3, No. 057,724, No. 3,038,805, No. 4,276,374, No. 4,297,439, No. 3,704,130, No. 4,782,013 Description, compounds described in JP-A-57-104926), thione compounds (for example, JP-A-53-82408, JP-A-55-77737, US Pat. No. 4,221,863) And tetrahalogenated thioureas described in JP-A-53-144319), and silver halide grains described in JP-A-57-202531 Mercapto compounds capable of accelerating growth, amine compounds (e.g., JP-A-54-100717) and the like.

  As a protective colloid used in preparing the emulsion used in the present invention and as a binder for other hydrophilic colloid layers, gelatin is advantageously used, but other hydrophilic colloids can also be used.

  For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives Various synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinylpyrazole, or a single or copolymer Substances can be used.

  As gelatin, in addition to lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin as described in Bull.Soc.Sci.Photo.Japan.No.16.P30 (1966) may be used. Hydrolysates and enzyme degradation products can also be used.

  The emulsion used in the present invention is preferably washed with water for desalting to form a newly prepared protective colloid dispersion. The temperature for washing with water can be selected according to the purpose, but is preferably selected within the range of 5 ° C to 50 ° C. Although pH at the time of water washing can also be chosen according to the objective, it is preferred to choose between 2-10. More preferably, it is the range of 3-8. Although pAg at the time of water washing can also be selected according to the objective, it is preferable to select between 5-10. The washing method can be selected from a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugal separation method, a coagulation sedimentation method, and an ion exchange method. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like can be selected.

  It may be useful to add a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031. In addition to S, Se, and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.

  The silver halide grains used in the present invention are at least one of chalcogen sensitization such as sulfur sensitization and selenium sensitization, noble metal sensitization such as gold sensitization and palladium sensitization, and reduction sensitization. It can be applied in any step of the emulsion production process. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are types that embed chemical sensitization nuclei inside the particles, types that embed in a shallow position from the particle surface, or types that make chemical sensitization nuclei on the surface. In the emulsion used in the present invention, the location of chemical sensitization nuclei can be selected according to the purpose, but generally preferred is the case where at least one chemical sensitization nucleus is formed in the vicinity of the surface.

One chemical sensitization that can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, either alone or in combination, by THJames, The Photographic Process, 4th edition, published by Macmillan, 1977. (THJames, The Theory of the Photographic Process, 4th ed, Macmillan, 1977) can be performed using active gelatin as described on pages 67-76, and Research Disclosure, 120, 1974. April 12008; Research Disclosure, Vol. 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, third 857,711, 3,901,714, 4,266,018, and 3,904,415, and British Patent 1,315,755. As described in each specification, it can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers at pAg 5-10, pH 5-8 and temperature 30-80 ° C. . In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, iridium and the like can be used, and gold sensitization, palladium sensitization and the combined use of both are particularly preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. Further, compounds described in US Pat. No. 5,049,485 are also preferably used. The palladium compound means a palladium divalent salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferable. Gold compounds and palladium compounds are preferably used in combination with thiocyanate or selenocyanate.

  Sulfur sensitizers include hypo, thiourea compounds, rhodanine compounds and U.S. Pat. Nos. 3,857,711, 4,266,018 and 4,054,457, The sulfur-containing compound described in each specification of 4,810,626 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers are U.S. Pat. Nos. 2,131,038, 3,411,914, and 3,554,757, and JP-A-58-126526. Gazette and the above-mentioned "Photo Emulsion Chemistry" by Duffin, pages 138 to 143.

The emulsion used in the present invention is preferably used in combination with gold sensitization. A preferable amount of the gold sensitizer is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol per mol of silver halide, and more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol. A preferred range for the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ mole per mole of silver halide. A preferable range of the thiocyan compound or selenocyan compound is 5 × 10 ⁻² to 1 × 10 ⁻⁶ mol per mol of silver halide.

The preferred amount of sulfur sensitizer used for the emulsion used in the present invention is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mole per mole of silver halide, more preferably 1 × 10 ^{−5 to} 5 × 10 ^-7 mol.

  Selenium sensitization is a preferred sensitizing method for the emulsion used in the present invention. In selenium sensitization, a known unstable selenium compound is used. Specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea), selenoketones Selenium compounds such as selenoamides can be used. Selenium sensitization may be preferably used in combination with sulfur sensitization, noble metal sensitization, or both.

  It is preferable to subject the silver halide emulsion used in the present invention to reduction sensitization during grain formation, after grain formation and before chemical sensitization, during chemical sensitization, or after chemical sensitization. Here, reduction sensitization means a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or ripening in a low pAg atmosphere called silver ripening, and a pH of 8 to 11 called high pH ripening. Any of the methods of growing or aging in the high pH atmosphere can be selected. Two or more methods can be used in combination.

  The method of adding a reduction sensitizer is a preferable method in that the level of reduction sensitization can be finely adjusted.

As reduction sensitizers, for example, stannous salts, ascorbic acid and derivatives thereof, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, and borane compounds are known. For reduction sensitization, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. As a reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferable compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but a range of 10 ⁻⁷ to 10 ⁻³ mol per mol of silver halide is appropriate.

  The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters, and amides and added during particle growth. Although it may be added to the reaction vessel in advance, a method of adding it at an appropriate time of particle growth is preferred. Alternatively, a reduction sensitizer may be added in advance to the water solubility of the water-soluble silver salt or water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also preferable to add the reduction sensitizer solution several times as the particle grows, or to add it continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion used in the present invention. The oxidizing agent for silver refers to a compound having an action of acting on metallic silver and converting it into silver ions. Particularly effective are compounds capable of converting extremely fine silver grains by-produced in the process of forming silver halide grains and chemical sensitization into silver ions. The silver ions generated here may form, for example, a silver salt that is hardly soluble in water such as silver halide, silver sulfide, or silver selenide, or a silver salt that is easily soluble in water such as silver nitrate. May be formed. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , Na ₄ P ₂ O ₇ .2H _{2). O 2, 2Na 2 SO 4 ·} H 2 O 2 · 2H 2 O), peroxy acid salt _{(e.g., K 2 S 2 O 8,} K 2 C 2 O 6, K 2 P 2 O 8), peroxy complex compound ( For _{example, K 2 [Ti (O 2} ) C 2 O 4] · 3H 2 O, 4K 2 SO 4 · Ti (O 2) OH · SO 4 · 2H 2 O, Na 3 [VO (O 2) (C 2 H ₄ ) ₂ ] · 6H ₂ O), permanganate (eg, KMnO ₄ ), oxyacid salts such as chromate (eg, K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine Perhalogenates (eg potassium periodate), high valent metal salts (eg potassium hexacyanoferric acid) and thio There are sulfonates.

  Examples of organic oxidizing agents include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (for example, N-bromosuccinimide, chloramine T, An example is chloramine B).

  Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidizing agents, and quinone organic oxidizing agents. It is a preferred embodiment to use the aforementioned reduction sensitization in combination with an oxidizing agent for silver. A method of applying reduction sensitization after using an oxidizing agent, a reverse method thereof, or a method of simultaneously coexisting both can be used. These methods can be selected and used in either the particle formation step or the chemical sensitization step.

  The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; for example, thioketo compounds such as oxadrine thione; azaindenes such as , Triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a, 7) chitraazaindenes), pentaazaindene Known as antifoggants or stabilizers, such as, it can be added to many compounds. For example, those described in US Pat. Nos. 3,954,474 and 3,982,947 and Japanese Patent Publication No. 52-28660 can be used. One preferred compound is the compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, water washing process, dispersion after water washing, chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to the original antifogging and stabilizing effect added during emulsion preparation, control the crystal wall of grains, reduce grain size, reduce grain solubility, control chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

  The photographic emulsion used in the present invention is preferably spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, for example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxador nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole Nuclei, benzimidazole nuclei and quinoline nuclei are applicable. These nuclei may have a substituent on the carbon atom.

  The merocyanine dye or the complex merocyanine dye has a ketomethylene structure as a nucleus, for example, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine A 5- or 6-membered heterocyclic nucleus of a nucleus or a thiobarbituric acid nucleus can be applied.

  These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703 377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patent 1,344,281, No. 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, and Japanese Patent Laid-Open Nos. 52-110618 and 52-109925.

  Along with the sensitizing dye, the emulsion itself may contain a dye having no spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization.

  Furthermore, in the present invention, it is also preferable to use in combination with a technique for improving the light absorption rate with a spectral sensitizing dye. For example, by utilizing intermolecular force, more sensitizing dyes can be adsorbed on the surface of silver halide grains than monolayer saturated adsorption (ie, single layer adsorption), or two or more separate conjugates can be covalently bonded. Adsorption of so-called linked dyes with linked chromophores. Among them, JP-A-10-239789, JP-A-11-133511, JP-A-2000-267216, JP-A-2000-275772, JP-A-2001-75222, JP-A-2001-75247. JP-A-2001-75221, JP-A-2001-75226, JP-A-2001-75223, JP-A-2001-255615, JP-A-2002-23294, JP-A-10-171058, No. 10-186559, JP-A-10-197980, JP-A 2000-81678, JP-A 2001-5132, JP-A 2001-166413, JP-A 2002-49113, JP-A 64-91134, JP-A-10-110107, JP-A-10 No. 171058, JP-A-10-226758, JP-A-10-307358, JP-A-10-307359, JP-A-10-310715, JP-A-2000-231174, JP-A-2000-231172. Publication, JP 2000-231173, JP 2001-356442, European Patent 985965A, European Patent 985964A, European Patent 985966A, European Patent 985967A, European Patent 1085372A No. 1, European Patent No. 1085373A, European Patent No. 1172688A, European Patent No. 1199595A, and European Patent No. 887700A1 are preferably used in combination. Furthermore, it is preferable to use in combination with the techniques described in JP-A-10-239789, JP-A-2001-75222, and JP-A-10-171058.

  The timing when the sensitizing dye is added to the emulsion may be at any stage of emulsion preparation that has been known to be useful so far. Most commonly, it is performed during the period after completion of chemical sensitization and before application, but as described in US Pat. Nos. 3,628,969 and 4,225,666, Spectral sensitization can be performed simultaneously with chemical sensitization by adding at the same time as the sensitizer, or can be performed prior to chemical sensitization as described in JP-A-58-113928. Spectral sensitization can be started by adding before completion of silver halide grain precipitation. Furthermore, as taught in U.S. Pat. No. 4,225,666, these said compounds are added separately, i.e. some of these compounds are added prior to chemical sensitization and the remainder It can be added after chemical sensitization, and may be any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 4,183,756.

The addition amount can be 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide, but about 5 × in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm. 10 ^{−5 to} 2 × 10 ⁻³ mol is effective.

  In the silver halide photographic light-sensitive material of the present invention, one or more light-sensitive layers are provided on a support. Moreover, a photosensitive layer can be provided on both sides, not limited to one side of the support. The light-sensitive material of the present invention is a black-and-white silver halide photographic light-sensitive material (for example, an X-ray light-sensitive material, a lith-type light-sensitive material, a black-and-white photographic negative film) or a color photographic light-sensitive material (for example, a color negative film, a color reversal film, a color film). Paper). Furthermore, it can also be used for photosensitive materials for diffusion transfer (for example, color diffusion transfer elements, silver salt diffusion transfer elements), photothermographic materials (black and white, color), and the like.

Hereinafter, the color photographic light-sensitive material will be described in detail, but the present invention is not limited to the embodiment described below.
The photosensitive material of the present invention is required to have at least one photosensitive layer on a support, and it is preferable to provide at least three photosensitive layers provided with different photosensitive areas. A typical example is a silver halide photographic light-sensitive material having at least three photosensitive layers composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity on a support. is there. The photosensitive layer is a unit photosensitive layer having color sensitivity to any one of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layer is generally arranged from the support side. The red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer are installed in this order. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched in the same color-sensitive layer.

A non-photosensitive layer such as an intermediate layer of each layer may be provided between the above-described silver halide photosensitive layers and in the uppermost layer and the lowermost layer.
In the intermediate layer, couplers and DIR compounds described in JP-A Nos. 61-43748, 59-113438, 59-113440, 61-20037, and 61-20038 are formed. It may be contained, and may contain a color mixing inhibitor as is usually used.

  A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion as described in West German Patent 1,121,470 or British Patent 923,045. A two-layer structure of layers can be preferably used. In general, it is preferable that the photosensitivity is gradually decreased toward the support, and a non-photosensitive layer may be provided between the halogen emulsion layers. Further, as described in JP-A-57-112751, 62-200350, 62-206541 and 62-206543, a low-sensitivity emulsion layer and a support on the side away from the support A high-sensitivity emulsion layer may be provided on the side close to.

As a specific example, from the side farthest from the support, for example, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / high sensitivity. Installed in the order of red photosensitive layer (RH) / low sensitivity red photosensitive layer (RL), BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH. can do.
Further, as described in JP-B-55-34932, the light-sensitive layer can be arranged in the order of blue photosensitive layer / GH / RH / GL / RL from the farthest side from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, the blue photosensitive layer / GL / RL / GH / RH may be installed in this order from the side farthest from the support.

  In addition, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree is arranged, and an arrangement composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even in the case of being composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitive emulsion layer from the side away from the support in the same color-sensitive layer. They may be arranged in the order of / high sensitivity emulsion layer / low sensitivity emulsion layer.

In addition, they may be arranged in the order of high sensitivity emulsion layer / low sensitivity emulsion layer / medium sensitivity emulsion layer, or low sensitivity emulsion layer / medium sensitivity emulsion layer / high sensitivity emulsion layer.
Further, the arrangement may be changed as described above even when there are four or more layers.
As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The above-mentioned various additives are used in the light-sensitive material according to the present invention, but various additives can be used depending on the purpose.
These additives are described in more detail in Research Disclosure Item 17643 (December 1978), Item 18716 (November 1979), and Item 308119 (December 1989). These are summarized in the table below.

Additive type RD17643 RD18716 RD308119
1 Chemical sensitizer page 23 page 648 right column page 996
2 Sensitivity increasing agent Same as above
3 Spectral sensitizer, pages 23 to 24, page 648, right column to 996, right to 998, right supersensitizer, page 649, right column
4 Brightener 24 pages 647 right column 998 right
5 Antifoggant, 24-25 pages 649, right column 998 right-1000 right and stabilizer
6 Light absorber, page 25-26, page 649, right column to 1003, left to 1003 right Filter dye, page 650, left column, UV absorber
7 Stain inhibitor Page 25 Right column 650 Left to right column 1002 Right
8 Dye image stabilizer 25 page 1002 right
9 Hardener page 26 page 651 left column 1004 right to 1005 left
10 Binder page 26 Same as above 1003 right to 1004 right
11 Plasticizer, Lubricant 27 pages 650 right column 1006 left to 1006 right
12 Coating aid, pages 26-27 Same as above 1005 Left to 1006 Left Surfactant
13 Static 27 pages Same as above 1006 Right to 1007 Left Anti-blocking agent
14 Matting agent 1008 left to 1009 left.

  In order to prevent deterioration of photographic performance due to formaldehyde gas, a compound that can be immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 is disclosed. It is preferably added to the light-sensitive material.

  Various color couplers can be used in the present invention, and specific examples thereof are the above-mentioned Research Disclosure No. 17643, VII-CG and No. 307105, described in the patents described in VII-CG.

  Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961. Each specification, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat. No. 3,973,968, No. 4,314,023 No. 4,511,649, European Patent Publication No. EP249,473A, etc. are preferable.

  The magenta coupler is preferably a 5-pyrazolone compound or a pyrazoloazole compound, such as U.S. Pat. Nos. 4,310,619, 4,351,897, European Patent Publication No. EP73,636, U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure no. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-35730, 55-118034, 60-185951, US Pat. No. 4, Particularly preferred are those described in the specifications of Nos. 500,630, 4,540,654, 4,556,630, and International Publication No. WO88 / 04795.

  Examples of cyan couplers include phenolic and naphtholic couplers, U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200. No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3 758, 308, 4,334, 011, 4,327, 173, West German Patent Publication 3,329,729, European Patent Publication EP 121,365A, No. 249,453A, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767. No. 4, 690, 889 , The No. 4,254,212, the respective specification No. 4,296,199, are preferred according to JP 61-42658 Patent Publication.

  Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320, No. 4,576,910, British Patent No. 2,102,137, and European Patent Publication No. EP41,188A.

  Examples of couplers in which the coloring dye has moderate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent Publication EP 96,570, West German Patent (published) ) No. 3,234,533 is preferred.

  Colored couplers for correcting unwanted absorption of chromogenic dyes are Research Disclosure No. No. 17643, VII-G, No. No. 307105, VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. No. 4,004,929, U.S. Pat. No. 4,138,258, British Patent No. 1 , 146, 368, and the like. In addition, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye emitted during coupling described in US Pat. No. 4,774,181, and a coupler described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye.

  Compounds that release photographically useful residues upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors include those described in RD17643, VII-F, and No. 1 above. 307105, patents described in paragraph VII-F, JP-A 57-151944, 57-154234, 60-184248, 63-37346, 63-37350, US Pat. , 248,962 and 4,782,012 are preferable.

  Examples of couplers that release a nucleating agent or a development accelerator in an image state during development include British Patent Nos. 2,097,140 and 2,131,188, and JP-A-59-157638 and 59. -170840 The thing of each gazette is preferable. Further, a fogging agent and a developing agent are obtained by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, and JP-A-1-45687. Also preferred are compounds that release accelerators, silver halide solvents and the like.

  Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and the like, US Pat. Nos. 4,283,472, 4,338, Multi-equivalent couplers described in each specification such as 393 and 4,310,618, and DIR redox compound releasing couplers described in JP-A-60-185950 and JP-A-62-24252 DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, couplers that release a dye that recovers after release described in European Patent Publications EP 173,302A and 313,308A, RD. No. No. 11449, No. 24241, bleach accelerator releasing coupler described in JP-A-61-201247, ligand releasing coupler described in US Pat. No. 4,555,477, JP-A-63-75747, etc. And couplers that emit fluorescent dyes described in US Pat. No. 4,774,181.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods.
Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027 and Japanese Patent Application Laid-Open No. 2003-149776.
Specific examples of high-boiling organic solvents having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate) Bis (2,4-di-tert-amylphenyl) phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); phosphoric acid or phosphonic acid Esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate Benzoates (eg 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate); amides (eg N, N-diethyldodecanamide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone); alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert-amylphenol); aliphatic carboxylic acid esters (eg, bis ( 2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (eg, N, N-dibutyl-2-butoxy-5-tert-octylanily) ); Hydrocarbons (e.g., can be exemplified paraffin, dodecylbenzene, and diisopropylnaphthalene). As the auxiliary solvent, for example, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples include, for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone. , Cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

  Examples of latex dispersion process steps, effects and impregnating latex are described in, for example, US Pat. No. 4,199,363, West German Patent Application (OLS) No. 2,541,274, and No. 2,541. 230.

  Examples of the color light-sensitive material of the present invention include phenethyl alcohol and those described in JP-A 63-257747, JP-A 62-272248, JP-A 1-80941, and the like, for example, 1,2-benzisothiazoline. Various preservatives or mildews such as -3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (4-thiazolyl) benzimidazole It is preferable to add an agent.

  The present invention can be applied to various color light-sensitive materials. For example, color negative films for general use or movies, color reversal films for slides or television, color paper, color positive film and color reversal paper can be given as representative examples. The present invention can be particularly preferably used for a film for color duplication.

  Suitable supports that can be used in the present invention include, for example, the RD. No. 17643, page 28, ibid. No. 18716, page 647, right column to page 648, left column, and 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the side having an emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and particularly preferably 16 μm or less. The membrane swelling speed T1 _{/ 2} is preferably 30 seconds or less, and more preferably 20 seconds or less. The film thickness here means a film thickness measured at 25 ° C. and a relative humidity of 55% (2 days). The film swelling rate T _1/2 can be measured according to a method known in the art, and for example, A. Green et al., Photographic Science and Engineering (Photogr. Sci. Eng. ), Vol. 19, No. 2, pp. 124-129. Note that T _1/2 is 90% of the maximum swollen film thickness that is reached when processed at 30 ° C. for 3 minutes and 15 seconds with a color developer, and is the time required to reach 1/2 of the saturated film thickness. Define.
The film swelling speed T1 _{/ 2} can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging conditions after coating.

  In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. This back layer preferably contains, for example, the above-described light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. . The swelling ratio of the back layer is preferably 150 to 500%.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pp. 28-29, ibid. No. 18716, page 651, left column to right column; 307105, pages 880-881, and can be developed by a conventional method.
The color developer used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly composed of an aromatic primary amine color developing agent. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N, N diethylaniline, 3-methyl -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl -Β-Toxyethylaniline, and sulfates, hydrochlorides or p-toluenesulfonates of these salts. Of these, sulfate of 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline is particularly preferable. These compounds may be used in combination of two or more depending on the purpose.

  Color developers include, for example, pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It is common to include a development inhibitor or an antifogging agent. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, catecholsulfonic acids; ethylene glycol, Organic solvents such as diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines; dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity imparting Agents: Various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid can be used. Examples of the chelating agent include ethylenediaminetetraacetic acid, nitrile triacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N- Typical examples include trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

  When reversal processing is performed, color development is usually performed after black and white development. This black-and-white developer includes, for example, dihydroxybenzenes such as hydroquinone, for example 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Known black-and-white developing agents can be used alone or in combination. The pH of these color developers and black-and-white developers is generally 9-12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 L or less per 1 square meter of the light-sensitive material. By reducing the bromide ion concentration in the replenishing solution, Below, also referred to as “mL”.) When reducing the replenishment amount, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing liquid with air.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below. That is,
Opening ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )]
The opening ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to a method of providing a shielding object such as a floating lid on the photographic processing liquid surface of the processing tank, a movable lid described in JP-A-1-82033 is used. Examples thereof include a slit developing method described in JP-A No. 63-216005. The reduction of the aperture ratio is preferably applied not only in both color development and black-and-white development but also in subsequent steps such as bleaching, bleach-fixing, fixing, washing and stabilization. Further, the replenishment amount can be reduced by using a means for suppressing the accumulation of bromide ions in the developer.

The color development time is usually set between 2 and 5 minutes, but the processing time can be further shortened by setting the temperature and pH to a high value and using the color developing agent at a high concentration.
The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleaching and fixing process) or may be performed individually. Further, in order to speed up the processing, a processing method of performing bleach-fixing processing after the bleaching processing may be used. Further, depending on the purpose, it is possible to carry out the treatment in two continuous bleach-fixing baths, the fixing treatment before the bleach-fixing treatment, or the bleaching treatment after the bleach-fixing treatment. As the bleaching agent, for example, a compound of a polyvalent metal such as iron (III), peracids (especially sodium persulfate is suitable for a color negative film for movies), quinones and nitro compounds are used. Typical bleaching agents include organic complex salts of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid. Complex salts with aminopolycarboxylic acids or complex salts with, for example, citric acid, tartaric acid and malic acid can be used. Of these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetic acid and 1,3-diaminopropanetetraacetic acid are the viewpoints of rapid processing and prevention of environmental pollution. To preferred. Furthermore, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these iron (III) complex salts of aminopolycarboxylic acids is usually from 4.0 to 8, but it can be processed at a lower pH in order to speed up the processing.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and their pre-bath, if necessary. Specific examples of useful bleach accelerators are described in the following specification:
For example, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, 2,059,988, JP-A-53-32736, 53-57831, 53 -37418, 53-72623, 53-95630, 53-95631, 53-104232, 53-124424, 53-141623, 53-18426, Research Publications Disclosure No. Compound having a mercapto group or disulfide group described in JP-A No. 17129 (July 1978); a thiazolidine derivative described in JP-A No. 51-140129; JP-B No. 45-8506, JP-A No. 52-20832 Nos. 53-32735, thiourea derivatives described in US Pat. No. 3,706,561, iodides described in West German Patent 1,127,715, JP-A-58-16235 Salts; polyoxyethylene compounds described in the specifications of West German Patent Nos. 966,410 and 2,748,430; polyamine compounds described in JP-B No. 45-8836; No. 49-59644, 53-94927, 54-35727, 55-26506, 58-163940 Compounds; bromide ion or the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect. In particular, US Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53- The compounds described in Japanese Patent No. 95630 are preferred. Furthermore, the compounds described in US Pat. No. 4,552,884 are also preferable. These bleach accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when a color light-sensitive material for photography is bleach-fixed.

  In addition to the above compounds, the bleaching solution or the bleach-fixing solution preferably contains an organic acid for the purpose of preventing bleaching stains. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specific examples include acetic acid, propionic acid, and hydroxyacetic acid.

  Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Of these, thiosulfate is generally used, and ammonium thiosulfate is most widely used. Further, a combination of thiosulfate and, for example, thiocyanate, thioether compound, or thiourea is also preferable. As a preservative for a fixing solution or a bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent Publication No. EP294,769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

  In the present invention, the fixing solution or bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, etc. It is preferable to add imidazoles in an amount of 0.1 to 10 mol / L.

The total desilvering time is preferably as short as possible without causing desilvering failure. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved, and the occurrence of stain after the treatment is effectively prevented.
In the desilvering step, it is preferable that the stirring is strengthened as much as possible. Specific methods for strengthening the stirring include a method of causing a jet of a processing solution to collide with the emulsion surface of a photosensitive material described in JP-A-62-183460, and a rotating means in JP-A-62-183461. To increase the stirring effect. Furthermore, the photosensitive material is moved while the wiper blade provided in the solution is in contact with the emulsion surface, and the emulsion surface is turbulent to improve the stirring effect, and the circulation flow rate of the entire processing solution is increased. The method of letting it be mentioned. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution, and the fixing solution. The improvement in stirring is considered to speed up the supply of the bleaching agent and the fixing agent into the emulsion film and consequently increase the desilvering rate. Further, the above stirring improving means is more effective when a bleaching accelerator is used, and the acceleration effect can be remarkably increased or the fixing inhibiting action can be eliminated by the bleaching accelerator.

  The automatic developing machine used for developing the photosensitive material of the present invention may have photosensitive material conveying means described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259. preferable. As described in JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the processing liquid from the pre-bath to the post-bath and is highly effective in preventing the performance deterioration of the processing liquid. Such an effect is particularly effective in shortening the processing time in each process and reducing the replenishment amount of the processing liquid.

  The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and / or a stabilization process after desilvering. The amount of water to be washed in the washing process depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), application, and replenishment such as washing water temperature, number of washing tanks (stages), countercurrent, and forward flow. A wide range can be set according to the system and other various conditions. Of these, the relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent system should be determined by the method described in Journal of the Society of Motion Picture and Television Engineers Vol. 64, pages 248-253 (May 1955). Can do.

  According to the multi-stage countercurrent system described in the above-mentioned document, the amount of water to be washed can be greatly reduced. However, bacteria are propagated due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. In addition, as described in JP-A-57-8542, for example, isothiazolone compounds, siabendazoles, chlorinated bactericides such as chlorinated sodium isocyanurate, and others such as benzotriazole, Hiroshi Horiguchi. "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan The disinfectant described in “Enamel Antibacterial Encyclopedia” (1986) can also be used.

  The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can also be variously set depending on, for example, the characteristics and application of the photosensitive material. In general, the washing water temperature and washing time are 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. A range is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the water washing. In such stabilization treatment, all known methods described in JP-A-57-8543, 58-14834, and 60-220345 can be used.

  Further, a stabilization treatment may be further performed following the water washing treatment. Examples thereof include a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow liquid accompanying the washing and / or replenishment of the stabilizing liquid can be reused in other processes such as a desilvering process.
For example, in the processing using an automatic developing machine, when each of the above processing solutions is concentrated by evaporation, it is preferable to correct the concentration by adding water.

  The silver halide color photographic light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate them, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in US Pat. No. 3,342,597, for example, US Pat. No. 3,342,599, Research Disclosure No. 14,850 and No. No. 15,159, Schiff base type compounds, And aldol compounds described in US Pat. No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development, if necessary. Typical compounds are described in, for example, JP-A Nos. 56-64339, 57-144547, and 58-115438.
The various processing liquids in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but the temperature is increased to accelerate the processing and shorten the processing time, or conversely, the temperature is lowered to achieve an improvement in image quality and stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat. No. 4,500,626, JP-A-60-133449, 59-218443, 61-238056, and European Patent Publication EP210. , 660A2 and the like can also be applied to photothermographic materials.
In addition, the silver halide color photographic light-sensitive material of the present invention is more effective when applied to a lens-fitted film unit described in Japanese Patent Publication No. 2-332615 and Japanese Utility Model Publication No. 3-39784. It is easy and effective.

Next, the magnetic recording layer preferably used in the present invention will be described.
The magnetic recording layer preferably used in the present invention is obtained by coating a support with an aqueous or organic solvent based coating liquid in which magnetic particles are dispersed in a binder.

Magnetic particles used in the present invention include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite, Co containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy Hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite and the like can be used. Co-coated ferromagnetic iron oxide such as Co-coated γFe ₂ O ₃ is preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. The specific surface area is preferably at least 20 m ² / g in S _BET, and particularly preferably equal to or greater than 30 m ² / g.

The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, and particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent on the surface thereof as described in JP-A-6-161032. Also, magnetic particles having a surface coated with inorganic or organic substances as described in JP-A-4-259911 and JP-A-5-81652 can be used.

  Examples of the binder used for the magnetic particles include thermoplastic resins, thermosetting resins, radiation curable resins, reactive resins, acids, alkalis or biodegradable polymers, and natural product weights described in JP-A-4-219469. Combinations (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above resin preferably has a Tg of -40 ° C to 300 ° C and a mass average molecular weight of 20,000 to 1,000,000. Examples of the binder include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose derivatives such as cellulose tripropionate, acrylic resins, and polyvinyl acetal resins. Gelatin is also preferred. Cellulose di (tri) acetate is particularly preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of isocyanate-based crosslinking agents include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and the like, and reaction products of these isocyanates with polyalcohol (for example, tolylene diene). Reaction product of 3 mol of isocyanate and 1 mol of trimethylolpropane), polyisocyanate formed by condensation of these isocyanates, and the like, for example, are described in JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin-type mill, an annular mill, etc. are preferable, and a combination is also preferable, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm, and still more preferably 0.3 μm to 3 μm. The mass ratio of the magnetic particles and the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ^2, preferably not 0.01 to 2 g / m ^2, more preferably at 0.02 to 0.5 g / m ^2. The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50, more preferably 0.03 to 0.20, and particularly preferably 0.04 to 0.15. The magnetic recording layer can be provided on the entire surface or in a stripe shape on the back surface of the photographic support by coating or printing. As a method for applying the magnetic recording layer, an air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extraction, etc. can be used. The coating solution described in Japanese Patent No. 341436 is preferable.

  The magnetic recording layer may have functions such as lubricity improvement, curl adjustment, antistatic, adhesion prevention, head polishing, etc., or another functional layer may be provided to give these functions. It is preferable that at least one of the particles is an abrasive of non-spherical inorganic particles having a Mohs hardness of 5 or more. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. The surface of these abrasives may be treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as that for the magnetic recording layer is preferable. Photosensitive materials having a magnetic recording layer are described in US 5,336,589, 5,250,404, 5,229,259, 5,215,874, EP 466,130.

  Next, the polyester support preferably used in the present invention will be described. For details including photosensitive materials, processing, cartridges, and examples described later, the published technical bulletin, public technical number 94-6023 (Invention Association; 19944.3). .15.). The polyester used in the present invention is formed using diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic as aromatic dicarboxylic acid Examples of the acid, isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of this polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 mol% to 100 mol% of 2,6-naphthalenedicarboxylic acid. Of these, polyethylene-2,6-naphthalate is particularly preferred. The range of mass average molecular weight is about 5,000 to 200,000. The Tg of the polyester of the present invention is preferably 50 ° C. or higher, more preferably 90 ° C. or higher.

Next, the polyester support is heat-treated at a heat treatment temperature of preferably 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg in order to make it difficult to cause curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. This heat treatment time is preferably 0.1 hours to 1500 hours, more preferably 0.5 hours to 200 hours. The heat treatment of the support may be performed in a roll shape or may be performed while being conveyed in a web shape. The surface may be improved by providing irregularities on the surface (for example, applying conductive inorganic fine particles such as SnO ₂ and Sb ₂ O ₅ ). Further, it is desirable to devise such as applying a knurl to the end portion and slightly raising only the end portion to prevent the winding portion from being cut off. These heat treatments may be carried out at any stage after forming the support, after the surface treatment, after applying the back layer (antistatic agent, slip agent, etc.) and after applying the undercoat. Preferred is after application of the antistatic agent.

  This polyester may be kneaded with an ultraviolet absorber. In order to prevent light piping, the purpose can be achieved by kneading dyes or pigments that are commercially available for polyesters such as Mitsubishi Kasei's Diaresin and Nippon Kayaku's Kayset.

  Next, in the present invention, it is preferable to perform a surface treatment in order to adhere the support and the photosensitive material constituting layer. Examples of the surface activation treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.

Next, the primer method will be described. It may be a single layer or two or more layers. As a binder for the undercoat layer, starting from a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Examples of compounds that swell the support include resorcin and p-chlorophenol. As the gelatin hardener for the undercoat layer, chromium salts (such as chromium alum), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine) Etc.), epichlorohydrin resins, active vinyl sulfone compounds and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

  In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include polymers containing carboxylic acids and carboxylates and sulfonates, cationic polymers, and ionic surfactant compounds.

Most preferred as the antistatic agent is at least one selected from ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , V ₂ O _5. The volume resistivity of the seed is 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. The particle size is 0.001 to 1.0 μm Crystalline metal oxide or a composite oxide thereof (Sb, P, B, In, S, Si, C, etc.), and also sol-like metal oxides or composite oxides thereof.

The content of the photosensitive material, 5 to 500 mg / m ² is preferably particularly preferably 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably 1/300 to 100/1, more preferably 1/100 to 100/5.

  The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used for both the photosensitive layer surface and the back surface. A preferable slip property is 0.25 or less and 0.01 or more in terms of dynamic friction coefficient. The measurement at this time represents a value when the stainless steel sphere having a diameter of 5 mm is conveyed at 60 cm / min (25 ° C., 60% RH). In this evaluation, even if the counterpart material is replaced with the photosensitive layer surface, the value is almost the same.

  Examples of slip agents that can be used in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and examples of polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, Styrylmethylsiloxane, polymethylphenylsiloxane, and the like can be used. As the additive layer, the outermost layer of the emulsion layer or the back layer is preferable. In particular, polydimethylsiloxane and esters having a long chain alkyl group are preferred.

  The light-sensitive material of the present invention preferably has a matting agent. The matting agent may be either the emulsion surface or the back surface, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and is preferably a combination of both. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, the particle size distribution is preferably narrower, and 90% or more of the total number of particles is preferably contained between 0.9 and 1.1 times the average particle size. . It is also preferable to add fine particles of 0.8 μm or less at the same time in order to improve the matting property, for example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm. )), Polystyrene particles (0.25 μm), and colloidal silica (0.03 μm).

  The support used in this example can be prepared by the method described in Example 1 of JP-A No. 2001-281815.

Next, the film cartridge used in the present invention will be described. The main material of the cartridge used in the present invention may be metal or synthetic plastic.
Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the cartridge may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations and betaine surfactants or polymers can be preferably used. These antistatic cartridges are described in JP-A Nos. 1-312537 and 1-312538. In particular, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, plastic patrone is manufactured using a plastic kneaded with carbon black or pigment to provide light shielding. The size of the patrone may be the current 135 size, and it is also effective to reduce the diameter of the 25 mm cartridge of the current 135 size to 22 mm or less in order to reduce the size of the camera. The volume of the cartridge case is 30 cm ³ or less, preferably 25 cm ³ or less. The mass of the plastic used for the cartridge and the cartridge case is preferably 5 to 15 g.

  Further, a patrone for rotating the spool and feeding the film may be used in the present invention. Alternatively, the film leading end may be housed in the cartridge main body, and the film leading end may be sent out from the port portion of the cartridge by rotating the spool shaft in the film feeding direction. These are disclosed in US 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development, or may be a photographic film that has been developed. Further, the raw film and the developed photographic film may be stored in the same new cartridge, or may be different cartridges.

The color photographic light-sensitive material of the present invention is also suitable as a negative film for an advanced photo system (hereinafter referred to as AP system), manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film), NEXIA A, NEXIA F, The film is processed into an AP system format such as NEXIA H (in order ISO 200/100/400) and stored in a dedicated cartridge. These AP system cartridge films are used by being loaded into an AP system camera such as FUJIFILM's EPION series (such as EPION 300Z).
Further, the color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as FUJIFILM Fuji Color Photographic Runn Super Slim and Photographic Rune ACE800.

  The film photographed by these is printed through the following process in the minilab system.

(1) Reception (carrying out the exposed cartridge film from the customer)
(2) Detach process (transfer film from cartridge to intermediate cartridge for development process)
(3) Film development (4) Rear touch process (return developed negative film back to original cartridge)
(5) Print (C / H / P3 type prints and index prints are automatically printed on color paper (preferably SUPER FA8 manufactured by Fuji Film))
(6) Verification / shipment (Cartridge and index print are verified by ID number and shipped together with the print)
As these systems, FUJIFILM Minilab Champion Super FA-298 / FA-278 / FA-258 / FA-238 and FUJIFILM Digital Lab System Frontier are preferred. Minilab champion film processors include FP922AL / FP562B / FP562B, AL / FP362B / FP362B, AL, and recommended processing chemicals are Fujicolor Justit CN-16L and CN-16Q. Examples of the printer processor include PP3008AR / PP3008A / PP1828AR / PP1828A / PP1258AR / PP1258A / PP728AR / PP728A, and recommended processing chemicals are Fujicolor Justit CP-47L and CP-40FAII.

  In the frontier system, a scanner & image processor SP-1000 and a laser printer & paper processor LP-1000P or a laser printer LP-1000W are used. The detacher used in the detaching step and the rear toucher used in the rear touching step are preferably DT200 / DT100 and AT200 / AT100 from Fuji Film, respectively.

  The AP system can also be enjoyed by a photo joy system centered on Fujifilm's digital image workstation Aladdin 1000. For example, it can be obtained by directly loading developed AP system cartridge film into Aladdin 1000 or inputting image information of negative film, positive film, and print using 35mm film scanner FE-550 or flat head scanner PE-550. Digital image data can be easily processed and edited. The data can be output as a print by a digital color printer NC-550AL using a light-fixing thermal color printing system, a photography 3000 using a laser exposure thermal development transfer system, or by an existing laboratory apparatus through a film recorder. Aladdin 1000 can also output digital information directly to a floppy disk (floppy: registered trademark) or Zip disk, or to a CD-R via a CD writer.

  On the other hand, at home, you can enjoy photos on a TV just by loading the developed AP system cartridge film into the Fujifilm photo player AP-1, and if you load it into the Fujifilm photo scanner AS-1, Image information can also be captured continuously at high speed. Moreover, in order to input a film, a print, or a three-dimensional object into a personal computer, FUJIFILM Photo Vision FV-10 / FV-5 can be used. Furthermore, image information recorded on a floppy disk, Zip disk, CD-R, or hard disk can be variously processed and enjoyed on a personal computer using Fujifilm's application software photo factory. In order to output a high-quality print from a personal computer, a digital color printer NC-2 / NC-2D manufactured by Fuji Film using a light fixing type thermal color printing method is suitable.

  To store the developed AP system cartridge film, Fuji Color Pocket Album AP-5 Pop L, AP-1 Pop L, AP-1 Pop KG or Cartridge File 16 is preferred.

  The features of the present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

(Synthesis Example 1: Synthesis of W-1)
Under a nitrogen atmosphere, 114.54 g (1.53 mol) of n-butanol and 32.90 g (0.77 mol) of NaOH were added to 200 mL of toluene, and the mixture was stirred at an internal temperature of 100 ° C. for 3 hours. The temperature was further raised, water was removed azeotropically, the temperature was lowered to 90 ° C., and 104.85 g (0.77 mol) of butanesultone was added dropwise over 1 hour. After the dropping, the reaction was carried out at an internal temperature of 95 ° C. for 3 hours. After cooling to room temperature, the reaction solution was dispersed in 1000 mL of acetonitrile and heated to reflux for 1 hour. The suspension was separated by filtration and vacuum dried to obtain 157.39 g (yield 88%) of W-1.

(Synthesis Example 2: Synthesis of W-12)
1-Butoxy-2-butanol (52.88 g, 0.40 mol) was dissolved in chloroform (500 mL), and a solution of chlorosulfonic acid (48.9 g, 0.42 mol) in chloroform (100 mL) was added dropwise over 30 minutes under ice cooling. Thereafter, a solution prepared by dissolving 82.0 g (0.82 mol) of sodium hydroxide in 1500 mL of ethanol was added. The reaction solution was concentrated under reduced pressure, and the concentrated solution was added to 4500 mL of acetonitrile to precipitate a solid. This was separated by suction filtration, and the solid was dried under reduced pressure to obtain 79.64 g (yield 85%) of the desired product.

(Synthesis Example 3: Synthesis of FS-113)
3-1 2- (2- (N, N-dimethylamino) ethylamino) succinic acid 1,4-di (3,3,4,4,5,5,6,6,6-nonafluorohexyl) Synthesis 500 g (0.82 mol) of succinic acid 1,4-di (3,3,4,4,5,5,6,6,6-nonafluorohexyl), 79.5 g of N, N-dimethylaminoethylamine (0.90 mol) and 11.3 g (0.08 mol) of potassium carbonate were dissolved in 500 mL of acetonitrile and heated to reflux for 45 minutes. Thereafter, the reaction solution was transferred to a separatory funnel, 2 L of ethyl acetate was added, the organic phase was washed with an aqueous sodium chloride solution (1.5 L), the organic layer was recovered, the organic solvent was distilled off under reduced pressure, and pale yellow As a result, 453 g (yield 79%) of the target compound was obtained.

3-2 Synthesis of FS-113 After adding 380 g (0.55 mol) of the above compound, 101.6 g (0.55 mmol) of methyl p-toluenesulfonate and 1500 mL of ethyl acetate, the mixture was heated under reflux for 2 hours, and then the insoluble matter was removed. It was filtered off and the filtrate was cooled in an ice bath with stirring. After a while, crystals precipitated from the filtrate. The obtained crystals were collected by filtration, washed with ethyl acetate, and dried under reduced pressure at 80 ° C. for 2 hours. 300 g (yield%) of the target compound was obtained as a colorless transparent solid.
The ¹ H-NMR data of the obtained compound is as follows.
¹ H-NMR (DMSO-d ₆ ): δ 2.50 (s, 3H), 2.61-2.73 (br, 8H), 3.07 (s, 9H) 3.33 (m, 2H), 3.66 (m, 1H), 4.30-4.40 (m, 4H), 7.11 (d, 2H) 7.48 (d, 2H)

(Synthesis Example 4: Synthesis of FS-201)
4-1 Synthesis of maleic acid di (3,3,4,4,5,5,6,6,6-nonafluorohexyl) Maleic anhydride 90.5 g (0.924 mol), 3,3,4,4 , 5,5,6,6,6-nonafluorohexanol 500 g (1.89 mol) and p-toluenesulfonic acid monohydrate 17.5 g (0.09 mol) in 1000 L of toluene by distilling off the water produced. The mixture was heated to reflux for 20 hours. Thereafter, the mixture was cooled to room temperature, toluene was added, the organic phase was washed with water, and the solvent was distilled off under reduced pressure to obtain 484 g (yield 86%) of the desired product as a transparent liquid.

4-2 Synthesis of FS-201 Maleic acid Di (3,3,4,4,5,5,6,6,6-nonafluorohexyl) 514 g (0.845 mol), sodium hydrogen sulfite 91.0 g (0. 875 mol) and 250 ml of water-ethanol (1/1 v / v) were added and the mixture was heated to reflux for 6 hours, followed by extraction with 500 mL of ethyl acetate and 120 mL of a saturated aqueous sodium chloride solution. The organic phase was recovered, sodium sulfate was added, and dehydration was performed. After removing sodium sulfate by filtration and concentrating the filtrate, 2.5 L of acetone was added and heated. The insoluble material was removed by filtration, and then cooled to 0 ° C., and 2.5 L of acetonitrile was slowly added. The precipitated solid was collected by filtration, and the obtained crystals were dried under reduced pressure at 80 ° C. to obtain 478 g (yield 79%) of the target compound as white crystals.
The ¹ H-NMR data of the obtained compound is as follows.
¹ H-NMR (DMSO-d ₆ ) δ 2.49-2.62 (m, 4H), 2.85-2.99 (m, 2H), 3.68 (dd, 1H), 4.23-4 .35 (m, 4H)

(Synthesis Example 5 Synthesis of FS-219)
5-1 Synthesis of itaconic acid di (3,3,4,4,5,5,6,6,6-nonafluorohexyl) Itaconic anhydride 13.5 g (0.12 mol), 3,3,4, 4,5,5,6,6,6-nonafluorohexanol (69.8 g, 0.26 mol) and p-toluenesulfonic acid monohydrate (1.14 g, 6 mmol) were added to 500 ml of toluene. The mixture was heated to reflux for 12 hours while distilling off. Thereafter, the mixture was cooled to room temperature, ethyl acetate was added, and the organic phase was washed with a 1 mol / liter aqueous sodium hydroxide solution and a saturated aqueous sodium chloride solution to obtain 51.3 g (69%) of the desired product as an oily compound. .

5-2 Synthesis of FS-19 Itaconic acid di (3,3,4,4,5,5,6,6,6-nonafluorohexyl) 20.0 g (32 mmol), sodium hydrogen sulfite 4.0 g (38 Mmol) and 25 ml of water-ethanol (1/1 v / v) were added and heated under reflux for 6 hours. Ethyl acetate was added, the organic phase was washed with a saturated aqueous sodium chloride solution, and the organic layer was dried over sodium sulfate. Thereafter, the solvent was concentrated under reduced pressure, followed by recrystallization with acetonitrile. The obtained crystals were dried under reduced pressure at 80 ° C. for 2 hours to obtain 20.6 g (yield 89%) of the target compound as white crystals.
The ¹ H-NMR data of the obtained compound is as follows.
¹ H-NMR (DMSO-d ₆ ) δ 2.49-2.78 (m, 5H), 3.04-3.13 (m, 2H), 3.47 (br, 2H) 4.23 (t, 4H)

(Synthesis Example 6: Synthesis of FS-302)
6-1 Synthesis of maleic acid (2-ethylhexyl) chloride While maintaining 4.1 g (20 mmol) of phosphorus pentachloride, 4.5 g (20 mmol) of mono (2-ethylhexyl) maleate manufactured by Aldrich at 30 ° C. or lower. It was dripped slowly. After completion of dropping, the mixture was stirred at room temperature for 1 hour. Then, it heated at 60 degreeC, pressure-reduced with the aspirator, the produced | generated phosphorus oxychloride was distilled off, and 4.5g (yield 92%) of brown oily compound maleic acid (2-ethylhexyl) chloride was obtained.

6-2 Synthesis of mono-2-ethylhexyl maleate mono 2,2,3,3,4,4,4-heptafluorobutyl 66.8 g of 2,2,3,3,4,4,4-heptafluorobutanol ( 0.334 mol) and 29.6 mL (0.367 mol) of pyridine in 180 mL of acetonitrile, cooled in an ice bath, and maintained at an internal temperature of 20 ° C. or less, 90.6 g (0. 367 mol) was added dropwise. After completion of dropping, the mixture is stirred at room temperature for 1 hour. Thereafter, 1000 mL of ethyl acetate was added, and the organic phase was washed with a 1 mol / L hydrochloric acid aqueous solution and a saturated sodium chloride aqueous solution. Then, the organic layer was recovered, the organic solvent was distilled off under reduced pressure, and silica gel column chromatography (hexane / chloroform: 10 / (0-7 / 3 v / v), purification operation was performed to obtain 80.3 g (yield 59%) of the target compound as a colorless transparent oily compound.

6-3 Synthesis of cidium mono 2-ethylhexyl mono 2,2,3,3,4,4,4-heptafluorobutyl sulfosuccinate (FS-302) Maleic acid mono 2-ethylhexyl mono 2,2,3,3 , 4,4,4-heptafluorobutyl 80.3 g (0.196 mol), sodium bisulfite 20.4 g (0.196 mol), 80 ml of water-ethanol (1/1 v / v) were added and heated to reflux for 10 hours. . Thereafter, 1000 mL of ethyl acetate was added, and the organic phase was washed with a saturated aqueous solution of sodium chloride. The organic layer was recovered, the organic solvent was distilled off under reduced pressure, and silica gel column chromatography (chloroform / methanol: 9/1 v / v). After purifying and washing the recovered organic phase with a saturated aqueous sodium chloride solution, the organic solvent was distilled off under reduced pressure to obtain 32 g (yield 32%) of the target compound as a colorless transparent solid.
The ¹ H-NMR data of the obtained compound is as follows.
¹ H-NMR (DMSO-d ₆ ) δ 0.81-0.87 (m, 6H), 1.24 (m, 8H), 1.50 (br, 1H), 2.77-2.99 (m , 2H), 3.63-3.71 (m, 1H), 3.86-3.98 (m, 3H), 4.62-4.84 (br, 1H)

(Synthesis Example 7: Synthesis of FS-312)
7-1 Synthesis of monodecyl maleate mono 3,3,4,4,5,5,6,6,6-nonafluorohexyl 3,3,4,4,5,5,6,6,6-nonafluoro 164.6 g (623 mmol) of hexanol and 49.3 mL (623 mmol) of pyridine were dissolved in 280 mL of chloroform, cooled in an ice bath, and 155.8 g (566 mmol) of monododecyl chloride maleate were added dropwise while maintaining the internal temperature at 20 ° C. or lower. . After completion of dropping, the mixture was stirred at room temperature for 1 hour. Thereafter, ethyl acetate was added, and the organic phase was washed with a 1 mol / L aqueous hydrochloric acid solution and a saturated aqueous sodium chloride solution. The organic layer was recovered, the organic solvent was distilled off under reduced pressure, and silica gel column chromatography (hexane / chloroform: 10/0 (7/3 v / v), and 48.2 g (yield 8%) of the target compound was obtained.

7-2 Synthesis of sodium monodecyl mono 3,3,4,4,5,5,6,6,6-nonafluorohexyl sulfosuccinate (FS-312) Monodecyl maleate mono 3,3,4,4,5 5,6,6,6-Nonafluorohexyl 48.0 g (90 mmol), sodium hydrogen sulfite 10.4 g (99 mmol), and water-ethanol (1/1 v / v) 50 mL were added and heated under reflux for 5 hours. Thereafter, ethyl acetate was added, and the organic phase was washed with a saturated aqueous sodium chloride solution. The organic layer was recovered, the organic solvent was distilled off under reduced pressure, and recrystallization was performed with acetonitrile. 12.5 g (yield 22%) of the target compound was obtained as a colorless transparent solid.
The ¹ H-NMR data of the obtained compound is as follows.
¹ H-NMR (DMSO-d ₆ ) δ 0.81-0.87 (t, 3H), 1.24 (m, 18H), 1.51 (br, 2H), 2.50-2.70 (m , 2H), 2.70-2.95 (m, 2H), 3.61-3.70 (m, 1H), 3.96 (m, 2H), 4.28 (ms, 2H)

(Synthesis Example 8: Synthesis of FS-309)
8-1 Synthesis of mono-2-ethylhexyl maleate mono 3,3,4,4,5,5,6,6,6-nonafluorohexyl 3,3,4,4,5,5,6,6,6 -515 g (1.95 mol) of nonafluorohexanol, 169 g (2.13 mol) of pyridine, 394 ml (3.89 mol) of triethylamine were dissolved in 1000 ml of chloroform, cooled in an ice bath, and maleic acid ( 530 g (2.14 mol) of 2-ethylhexyl) chloride was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1 hour. Thereafter, chloroform was added, and the organic phase was washed with water and a saturated aqueous sodium chloride solution. Then, the organic layer was recovered, the organic solvent was distilled off under reduced pressure, and silica gel column chromatography (hexane / chloroform: 10/0 to 7/3 v / The purification operation was carried out in v) to obtain 508 g (yield 50%) of the colorless and transparent target compound.

8-2 Synthesis of sodium (mono-2-ethylhexyl) (mono 3,3,4,4,5,5,6,6,6-nonafluorohexyl) sulfosuccinate (FS-309) Maleic acid (mono-2- Ethyl hexyl) (mono 3,3,4,4,5,5,6,6,6-nonafluorohexyl) 137.5 g (0.29 mol), sodium hydrogen sulfite 33.2 g (0.32 mol), water-ethanol 140 ml of (1/1 v / v) was added and heated to reflux for 2 hours. Thereafter, 1000 ml of ethyl acetate was added, and the organic phase was washed with a saturated aqueous solution of sodium chloride. Then, the organic layer was recovered, the organic solvent was distilled off under reduced pressure, recrystallization operation was performed with 800 mL of toluene, and crystals were formed by cooling in an ice bath. Precipitated. Finally, the crystals were separated by filtration to obtain 140 g (yield 84%) of a colorless and transparent target compound.
¹ H-NMR (DMSO-d ₆ ) δ 0.82-0.93 (m, 6H), 1.13-1.32 (m, 8H), 1.50 (br, 1H), 2.57-2 .65 (m, 2H), 2.84-2.98 (m, 2H), 3.63-3.68 (m, 1H), 3.90 (d, 2H), 4.30 (m, 2H) )

(Synthesis Example 9: Synthesis of FS-332)
9-1 Synthesis of mono-2-ethylhexyl maleate mono (1,1,1,3,3,3-hexafluoro-2-propyl) 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) 33.7 g (201 mmol) and 17.9 mL (220 mmol) of pyridine were dissolved in 80 mL of acetonitrile, cooled in an ice bath, and maintained at an internal temperature of 20 ° C. or lower, 41.8 g (220 mmol) of maleic acid mono-2-ethylhexyl chloride. ) Added dropwise. After completion of dropping, the mixture is stirred at room temperature for 1 hour. Thereafter, ethyl acetate was added, and the organic phase was washed with a 1 mol / L aqueous hydrochloric acid solution and a saturated aqueous sodium chloride solution. The organic layer was recovered, the organic solvent was distilled off under reduced pressure, and silica gel column chromatography (hexane / chloroform: 10/0 (7/3 v / v), and 10.6 g (yield 14%) of the target compound was obtained as a colorless transparent oily compound.

9-2 Synthesis of FS-332 Mono-2-ethylhexyl maleate (1,1,1,3,3,3-hexafluoro-2-propyl) 10.6 g (28 mmol), sodium hydrogen sulfite 3.2 g (31 mmol) ) And 10 mL of water-ethanol (1/1 v / v) were added and heated to reflux for 10 hours. Thereafter, ethyl acetate was added, and the organic phase was washed with a saturated aqueous sodium chloride solution. The organic layer was recovered, the organic solvent was distilled off under reduced pressure, and recrystallization was performed with acetonitrile. 1.7 g (yield 13%) of the target compound was obtained as a colorless and transparent solid.
The ¹ H-NMR data of the obtained compound is as follows.
¹ H-NMR (DMSO-d ₆ ) δ 0.81-0.87 (m, 6H), 1.25 (m, 8H), 1.50 (br, 1H), 2.73-2.85 (m , 2H), 3.59 (m, 1H), 3.85-3.90 (m, 2H), 12.23 (br, 1H)

Example 1
Silver halide emulsions Em-A to Em-O described in Table 1 below were prepared with reference to the process for producing Em-A to Em-O described in Example 1 of JP-A-2001-281815.

  As a result of observation using a high-voltage electron microscope, dislocation lines as described in JP-A-3-237450 were observed in the tabular grains in Table 1.

(Preparation of sample 001)
Each layer having the following composition was coated on the triacetyl cellulose support to form a color negative film (samples 001 to 014).

(Composition of photosensitive layer)
The main materials used in each layer are classified as follows:
ExC: Cyan coupler UV: Ultraviolet absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardener (Specific compounds are described below, followed by a numerical value, followed by a symbol, The chemical formula is mentioned).

The number corresponding to each component indicates the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver.

First layer (first antihalation layer)
Black colloidal silver Silver 0.130
0.07 μm silver iodobromide emulsion Silver 0.008
Gelatin 0.900
ExC-1 0.002
ExC-3 0.002
Cpd-2 0.001
HBS-1 0.005
HBS-2 0.002
F-8 0.001
Second layer (second antihalation layer)
Black colloidal silver Silver 0.030
Gelatin 0.425
ExF-1 0.002
Solid disperse dye ExF-9 0.120
HBS-1 0.074
F-8 0.001
Third layer (intermediate layer)
Cpd-1 0.080
HBS-1 0.042
Gelatin 0.300

Fourth layer (low sensitivity red sensitive emulsion layer)
Em-D Silver 0.577
Em-C Silver 0.347
ExC-1 0.233
ExC-2 0.026
ExC-3 0.129
ExC-4 0.155
ExC-5 0.029
ExC-6 0.013
Cpd-2 0.025
Cpd-4 0.025
ExC-8 0.050
HBS-1 0.114
HBS-5 0.038
Gelatin 1.474
5th layer (medium sensitivity red sensitive emulsion layer)
Em-B Silver 0.731
Em-C Silver 0.181
ExC-1 0.154
ExC-2 0.037
ExC-3 0.018
ExC-4 0.103
ExC-5 0.037
ExC-6 0.050
Cpd-2 0.036
Cpd-4 0.028
Cpd-6 0.060
ExC-7 0.010
HBS-1 0.129
Gelatin 1.086
6th layer (high sensitivity red sensitive emulsion layer)
Em-A Silver 1.050
ExC-1 0.072
ExC-3 0.035
ExC-10 0.080
Cpd-2 0.064
Cpd-4 0.077
Cpd-6 0.060
ExC-7 0.040
HBS-1 0.329
HBS-2 0.120
Gelatin 1.245

7th layer (intermediate layer)
Cpd-1 0.094
Cpd-9 0.369
Solid disperse dye ExF-4 0.030
HBS-1 0.049
Polyethyl acrylate latex 0.088
Gelatin 0.886
Eighth layer (a layer that gives a layered effect to the red sensitive layer)
Em-J Silver 0.400
Em-K Silver 0.100
Cpd-4 0.030
ExM-2 0.057
ExM-3 0.016
ExM-4 0.051
ExY-1 0.008
ExY-6 0.042
ExC-9 0.011
HBS-1 0.090
HBS-3 0.003
HBS-5 0.030
Gelatin 0.610
9th layer (low sensitivity green sensitive emulsion layer)
Em-H Silver 0.200
Em-G Silver 0.120
Em-I Silver 0.230
ExM-2 0.378
ExM-3 0.047
ExY-1 0.009
ExC-9 0.007
HBS-1 0.098
HBS-3 0.010
HBS-4 0.077
HBS-5 0.548
Cpd-5 0.010
Gelatin 1.470

10th layer (medium sensitive green sensitive emulsion layer)
Em-F Silver 0.336
ExM-2 0.049
ExM-3 0.035
ExM-4 0.014
ExY-1 0.003
ExY-5 0.006
ExC-6 0.007
ExC-8 0.010
ExC-9 0.012
HBS-1 0.065
HBS-3 0.002
HBS-5 0.020
Cpd-5 0.004
Gelatin 0.446
11th layer (High sensitivity green sensitive emulsion layer)
Em-E silver 0.593
Em-G 0.240
ExC-7 0.010
ExM-1 0.022
ExM-2 0.045
ExM-3 0.014
ExM-4 0.010
ExM-5 0.010
Cpd-3 0.004
Cpd-4 0.007
Cpd-5 0.010
HBS-1 0.148
HBS-5 0.037
Polyethyl acrylate latex 0.099
Gelatin 0.939
12th layer (yellow filter layer)
Cpd-1 0.094
Solid disperse dye ExF-2 0.150
Solid disperse dye ExF-5 0.010
Oil-soluble dye ExF-7 0.010
HBS-1 0.049
Gelatin 0.630

13th layer (low sensitivity blue sensitive emulsion layer)
Em-O Silver 0.070
Em-M Silver 0.504
Em-N Silver 0.090
ExC-1 0.048
ExY-1 0.012
ExY-2 0.350
ExY-6 0.060
ExY-7 0.300
ExC-9 0.012
Cpd-2 0.100
Cpd-3 0.004
HBS-1 0.222
HBS-5 0.074
Gelatin 2.058
14th layer (high sensitivity blue-sensitive emulsion layer)
Em-L Silver 0.900
ExY-2 0.100
ExY-7 0.100
Cpd-2 0.075
Cpd-3 0.001
HBS-1 0.071
Gelatin 0.678

15th layer (first protective layer)
0.07 μm silver iodobromide emulsion Silver 0.280
UV-1 0.100
UV-2 0.060
UV-3 0.095
UV-4 0.013
UV-5 0.200
F-11 0.009
S-1 0.086
HBS-1 0.175
HBS-4 0.050
Gelatin 1.984
16th layer (second protective layer)
H-1 0.400
B-1 (diameter 1.7 μm) 0.050
B-2 (diameter 1.7 μm) 0.150
B-3 0.050
Surfactant W-105 0.025
Surfactant W-107 0.009
Compounds listed in Table 2 0.060
S-1 0.200
Gelatin 0.750
Furthermore, in order to improve storage stability, processability, pressure resistance, antibacterial / antibacterial properties, antistatic properties and coatability as appropriate for each layer, B-4 to B-6, F-1 to F-17 and Lead salts, platinum salts, iridium salts and rhodium salts.

Preparation of dispersion of organic solid disperse dye (ExF-2 of 12th layer) Wet cake of ExF-2 (containing 17.6% by mass of water) 2.800 kg
Sodium octylphenyldiethoxymethanesulfonate
(31 mass% aqueous solution) 0.376 kg
F-15 (7% aqueous solution) 0.011 kg
4.020 kg of water
Total 7.210kg
(Adjusted to pH = 7.2 with NaOH)
After the slurry having the above composition is stirred and roughly dispersed by a dissolver, it is dispersed using an agitator mill LMK-4 at a peripheral speed of 10 m / s, a discharge rate of 0.6 kg / min, and a filling rate of zirconia beads having a diameter of 0.3 mm of 80%. Dispersion was performed until the absorbance ratio of the liquid reached 0.29 to obtain a solid fine particle dispersion. The average particle size of the fine dye particles was 0.29 μm.

  Similarly, solid dispersions of ExF-4 and ExF-9 were obtained. The average particle size of the fine dye particles was 0.28 μm and 0.49 μm, respectively. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of European Patent No. 549,489A. The average particle size was 0.06 μm.

  Hereinafter, compounds used for preparing each layer are shown.

The prepared samples 001 to 014 were evaluated for storage stability and developer stains.
(Evaluation of storage stability)
The samples 001 to 014 were subjected to hardening treatment under conditions of a temperature of 40 ° C. and a relative humidity of 70%. Thereafter, the film was exposed for 1/100 second through a gelatin filter SC-39 (long wavelength light transmission filter having a cut-off wavelength of 390 nm) and a continuous wedge manufactured by FUJIFILM Corporation. Development was performed as follows using an automatic processor FP-360B manufactured by Fuji Photo Film Co., Ltd. In addition, the overflow solution of the bleaching bath was remodeled so as not to flow to the rear bath but to discharge all to the waste liquid tank. This FP-360B is equipped with the evaporation correction means described in JIII Journal of Technical Disclosure No. 94-4992. The yellow density of each sample was measured, and the logarithm of the reciprocal of the exposure amount from Dmin to +0.5 was obtained as the relative sensitivity. In addition to these, another set of samples 001 to 014 was subjected to the same hardening treatment as described above, then stored for 7 days at a temperature of 50 ° C. and a relative humidity of 80%, and then exposed and developed in the same manner as described above. The sensitivity was obtained in the same manner as described above. Then, the difference between the relative sensitivity immediately after the dura mater and the relative sensitivity after storage over time was determined and shown in Table 2 as storability.

(Evaluation of developer stain)
Samples 001 to 014 are processed into an advanced photo system format, loaded in a special cartridge, and taken in daylight to photograph trees and flowers and people in 1000 color developing solutions described later After the treatment, insoluble matters in the developer were observed, and the results are shown in Table 2 as developer stains.

  The treatment process and the treatment liquid composition are shown below.

(Processing process)
Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ℃ 20 mL 11.5 L
Whitening 50 seconds 38.0 ℃ 5 mL 5L
Fixing (1) 50 seconds 38.0 ℃ ─ 5L
Fixing (2) 50 seconds 38.0 ℃ 8 mL 5L
Washing with water 30 seconds 38.0 ℃ 17 mL 3L
Stable (1) 20 seconds 38.0 ℃ ─ 3L
Stable (2) 20 seconds 38.0 ℃ 15 mL 3L
Dry 1 min 30 sec 60.0 ° C
* Replenishment amount per photosensitive material 35mm width 1.1m (24Ex. 1 equivalent).

  The stabilizing solution and the fixing solution were counter-current from (2) to (1), and all of the overflow solution of washing water was introduced into the fixing bath (2). The amount of developer brought into the bleaching step, the amount of bleaching solution brought into the fixing step, and the amount of fixing solution brought into the water washing step were 2.5 mL and 2.0 mL, respectively, per photosensitive material 35 mm width 1.1 m, 2.0 mL. In addition, the crossover time is 6 seconds, and this time is included in the processing time of the previous process.

Open area 100 cm ² in the color developing solution in the processor, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

  The composition of the treatment liquid is shown below.

(Color developer) Tank solution (g) Replenisher (g)
Diethylenetriaminepentaacetic acid 3.0 3.0
Catechol-3,5-disulfonic acid disodium 0.3 0.3
Sodium sulfite 3.9 5.3
Potassium carbonate 39.0 39.0
Disodium-N, N-bis (2-sulfonateethyl) hydroxylamine 1.5 2.0
Potassium bromide 1.3 0.3
Potassium iodide 1.3mg −
4-hydroxy-6-methyl-1,3
3a, 7-tetrazaindene 0.05-
Hydroxylamine sulfate 2.4 3.3
2-Methyl-4- [N-ethyl-N-
(Β-hydroxyethyl) amino]
Aniline sulfate 4.5 6.5
Add water 1.0L 1.0L
pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18

(Bleaching solution) Tank solution (g) Replenisher solution (g)
1,3-diaminopropanetetraacetic acid ferric ammonium monohydrate 113 170
Ammonium bromide 70 105
Ammonium nitrate 14 21
Succinic acid 34 51
Maleic acid 28 42
Add water 1.0L 1.0L
pH [adjusted with aqueous ammonia] 4.6 4.0

(Fixing (1) Tank liquid)
5 to 95 (volume ratio) mixture of the above bleach tank solution and the following fixing tank solution.

(PH 6.8)
(Fixing (2)) Tank liquid (g) Replenisher (g)
Ammonium thiosulfate aqueous solution 240 mL 720 mL
(750g / L)
Imidazole 7 21
Ammonium methanethiosulfonate 5 15
Ammonium methanesulfinate 10 30
Ethylenediaminetetraacetic acid 13 39
Add water 1.0L 1.0L
pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45

(Washing water)
Tap water is passed through a mixed bed column packed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IR-400). Then, the calcium and magnesium ion concentrations were adjusted to 3 mg / L or less, and then sodium isocyanurate dichloride 20 mg / L and sodium sulfate 150 mg / L were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Tank fluid and replenisher common (Unit: g)
Sodium p-toluenesulfinate 0.03
Polyoxyethylene-p-monononylphenyl ether 0.2
(Average polymerization degree 10)
1,2-Benzisothiazoline-3-one sodium 0.10
Ethylenediaminetetraacetic acid disodium salt 0.05
1,2,4-triazole 1.3
1,4-bis (1,2,4-triazole-1-
Ilmethyl) piperazine 0.75
Add water and add 1.0L
pH 8.5

  Table 2 shows the storage stability of samples 001 to 014 and the results of developer contamination.

  As is clear from Table 2, the photosensitive material containing the compound represented by the general formula (1) of the present invention has little developer stain and storage stability (small decrease in sensitivity when stored under high humidity). ).

(Example 2)
In the sample 202 of Example 4 of JP 2001-159799 A, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, it was a silver iodobromide or silver iodochlorobromide tabular grain having a (111) plane as the main plane, and the variation coefficient of equivalent circle equivalent diameter was 40% or less. Circle equivalent diameter of 3.5 μm or more, grain thickness of 0.25 μm or less, silver iodide content of 2 mol% or more and 6 mol% or less, silver chloride content of 3 mol or less, and multiple distribution of silver iodide distribution of five or more layers Also in a light-sensitive material using an emulsion containing tabular grains having a structure, a sample in which the compound represented by the general formula (1) and the fluorosurfactant of the present invention are used is the same as the sample of the present invention of Example 1. It was confirmed that an excellent effect was exhibited.

(Example 3)
In Sample 905 of Example 7 of JP-A-2000-347336, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, the compound represented by the general formula (1) and the fluorosurfactant of the present invention were also used in a photosensitive material having inorganic fine particles in the dispersion medium phase of the emulsion. It was confirmed that the sample showed the same excellent effect as the sample of the present invention of Example 1.

Example 4
In Sample 904 of Example 9 of JP-A-11-295832, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was carried out, a tabular grain having an aspect ratio of 3 or more, comprising a high iodine layer formed by rapidly generating iodide ions from an iodide ion releasing agent and containing a metal complex Also in the light-sensitive material using the emulsion containing, the sample in which the compound represented by the general formula (1) and the fluorosurfactant of the present invention are used exhibits the same excellent effect as the sample of the present invention of Example 1. It was confirmed.

(Example 5)
In Sample 222 of Example 8 of JP 2000-321698 A, the sixteenth layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, the aspect ratio was 8 or more, the average iodine content was 2 moles or more, the number of dislocation lines was 10 or more per particle, and the variation coefficient of the interparticle iodine distribution was 20 %, The sample using the compound represented by the general formula (1) and the fluorosurfactant of the present invention together is the same as the sample of the present invention of Example 1. It was confirmed that the excellent effect was exhibited.

(Example 6)
In the sample 109 of Example 1 of Japanese Patent Laid-Open No. 2000-231175, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, a sample using the compound represented by the general formula (1) and the fluorosurfactant of the present invention was also used in a photosensitive material containing a Pd (II) complex. It was confirmed that the same excellent effect as that of the inventive sample of Example 1 was exhibited.

(Example 7)
In the sample 302 of Example 3 of Japanese Patent Laid-Open No. 2001-324773, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, the compound represented by the general formula (1) and the fluorine-based interface of the present invention were also used in the light-sensitive material using an emulsion prepared in the presence of a halogen oxoacid salt. It was confirmed that the sample combined with the activator showed the same excellent effect as the sample of the present invention of Example 1.

(Example 8)
In the samples 001 to 014 of Example 1, the infrared absorbing dyes (62), (63), (64), (72), (74), and (87) of Japanese Patent Application Laid-Open No. 9-96891 are used. A sample was prepared in the same manner as in Example 1 except that it was introduced into two layers, and the same evaluation as in Example 1 was performed. Even when an infrared-absorbing dye is introduced, the sample using the compound represented by the general formula (1) and the fluorosurfactant of the present invention can exhibit the same excellent effect as the sample of the present invention of Example 1. confirmed.

Example 9
In Sample 403 of Example 4 of JP-A-2001-228572, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, it was a silver iodobromide or silver iodochlorobromide tabular grain having a (111) plane as the main surface, and the variation coefficient of the equivalent circle equivalent diameter distribution was 3 to 40%. Also in a photosensitive material using an emulsion containing tabular grains having an equivalent circle equivalent diameter of 1.0 μm or more and a grain thickness of 0.10 μm or less and lacking some of the sides and corners, it is represented by the general formula (1). It was confirmed that the sample in which the compound to be used and the fluorosurfactant of the present invention were used together showed the same excellent effect as the sample of the present invention of Example 1.

(Example 10)
In the sample of Example 6 of JP-A-2001-264911, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, it was a silver iodobromide or silver iodochlorobromide tabular grain having a parallel (111) plane as the main surface, and the variation coefficient of the equivalent circle equivalent diameter distribution was 40%. The equivalent circle equivalent diameter is 1.0 μm or more and the grain thickness is 0.10 μm or less, has a specific silver iodide content structure, has 5 or more dislocation lines per grain in the grain outer periphery, Further, in the light-sensitive material using an emulsion containing tabular grains having a hole trapping zone, a sample in which the compound represented by the general formula (1) and the fluorosurfactant of the present invention are used together is the present invention of Example 1. It was confirmed that the same excellent effect as the sample was exhibited.

(Example 11)
In Sample 713 of Example 7 of JP-A-2001-281778, the 16th layer of Example 1 was formed instead of the second protective layer. The same evaluation as in Example 1 was conducted. As a result, silver iodobromide or silver iodochlorobromide tabular grains having a thickness of 0.1 μm or less having an electron trapping zone and no annual ring structure observed in the grains were observed. Even in a light-sensitive material using an emulsion containing tabular grains having a silver halide phase, a sample in which the compound represented by the general formula (1) and the fluorosurfactant of the present invention are used together is the sample of the present invention of Example 1. It was confirmed that the same excellent effect was shown.

(Example 12)
In the sample 205 of Example 2 of Japanese Patent Laid-Open No. 2001-296627, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, a photosensitive material using an emulsion in which the formation of non-tabular grains produced by the preparation of tabular grains, particularly the formation of rod-shaped grains was reduced, was also represented by the general formula (1). It was confirmed that the sample using a combination of the above compound and the fluorosurfactant of the present invention showed the same excellent effect as the sample of the present invention of Example 1.

(Example 13)
In the sample 303 of Example 3 of JP-A-2002-169240, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, it was a silver iodobromide or silver iodochlorobromide tabular grain having a (111) plane as the main surface, and the variation coefficient of the equivalent circle equivalent diameter distribution was 3 to 40%. A photosensitive material using an emulsion containing tabular grains having an equivalent circle equivalent diameter of 1.0 μm or more and a grain thickness of 0.10 μm or less and lacking a part of sides or corners is also represented by the general formula (1). It was confirmed that the sample in which the compound to be used and the fluorosurfactant of the present invention were used together showed the same excellent effect as the sample of the present invention of Example 1.

(Example 14)
In Sample 205 of Example 2 of Japanese Patent Laid-Open No. 2001-255613, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, silver iodobromide or silver iodochlorobromide tabular grains having a (111) plane as the main surface, the equivalent circular equivalent diameter was 1.0 μm or more, and the grain thickness was An emulsion containing tabular grains having a core thickness of 0.10 μm or less, a core portion substantially free of dislocation lines and a shell portion including dislocation lines, and having a shell thickness of 0.01 μm or more perpendicular to the main plane was used. Also in the light-sensitive material, it was confirmed that the sample in which the compound represented by the general formula (1) and the fluorosurfactant of the present invention were used together showed the same excellent effect as the sample of the present invention of Example 1.

(Example 15)
In the sample 304 of Example 3 of JP-A-2002-268162, the 16th layer of Example 1 was formed instead of the second protective layer. The same evaluation as in Example 1 was conducted. As a result, it was a silver iodobromide or silver iodochlorobromide tabular grain having a (111) plane as a main surface and two parallel twin planes, and the grain thickness was 0 .. 12 μm or less, and an emulsion containing tabular grains having a high silver iodide content phase on either the upper side or the lower side of the region sandwiched between two twin planes in the grain fringe portion was used Also in the light-sensitive material, it was confirmed that the sample in which the compound represented by the general formula (1) and the fluorosurfactant of the present invention were used together showed the same excellent effect as the sample of the present invention of Example 1.

(Example 16)
In Sample 209 of Example 3 of Japanese Patent Laid-Open No. 2001-235821, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, the silver iodochlorobromide tabular grains having the (111) plane as the main surface were hexagonal tabular grains having a maximum side length / minimum side length ratio of 2 or less, Each has only one epitaxial junction at the six apexes of the hexagon, and the silver chloride content is 1 mol% to 6 mol%, and the silver iodide content is 0.5 mol% to 10 mol%. Also in the light-sensitive material using the emulsion containing the following tabular grains, the sample using the compound represented by the general formula (1) and the fluorosurfactant of the present invention is as excellent as the sample of the present invention of Example 1. It was confirmed to show the effect.

(Example 17)
In the sample 202 of Example 4 of JP-A-2002-169241, the 16th layer of Example 1 was formed instead of the second protective layer. The same evaluation as in Example 1 was conducted. As a result, the silver iodochlorobromide tabular grains having the (111) plane as the main surface, the epitaxial junction containing at least one dislocation line at at least one apex portion. Also in the light-sensitive material using the emulsion containing tabular grains having the above, the sample using the compound represented by the general formula (1) and the fluorosurfactant of the present invention is as excellent as the sample of the present invention of Example 1. It was confirmed to show the effect.

(Example 18)
In Example 3 of JP-A-2002-278008, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, it was a silver iodochlorobromide tabular grain having a (111) face as the main surface, and the silver chloride content of at least one vertex of the hexagon was 5 to 25 mol%. Even in a light-sensitive material using an emulsion containing tabular grains having the following epitaxial junction, a sample in which the compound represented by the general formula (1) and the fluorosurfactant of the present invention are used in combination is a sample of the present invention of Example 1. It was confirmed that the same excellent effect was exhibited.

(Example 19)
In Sample 303 of Example 3 of JP-A-2002-169239, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, silver iodochlorobromide tabular grains having a (111) plane as the main surface, an equivalent circular equivalent diameter of 3 μm or more, an aspect ratio of 8 or more, and an epitaxial junction were obtained. Also in the light-sensitive material using the emulsion containing the tabular grains, the sample using the compound represented by the general formula (1) and the fluorosurfactant of the present invention was as excellent as the sample of the present invention of Example 1. It was confirmed to show an effect.

(Example 20)
In Sample 101 of Example 5 of JP-A-7-134351, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, the compound represented by the general formula (1) and the fluorosurfactant of the present invention were also used in a photosensitive material containing a hydrazine compound as an adsorbing group for silver halide. It was confirmed that the sample used in combination showed the same excellent effect as the sample of the present invention of Example 1.

(Example 21)
In Sample 602 of Example 6 of Japanese Patent Laid-Open No. 2000-250157, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, the compound represented by the general formula (1) and the fluorosurfactant of the present invention were also used in a photosensitive material using an emulsion containing a bispyridinium salt compound. It was confirmed that the sample showed the same excellent effect as the sample of the present invention of Example 1.

(Example 22)
In Sample 218 of Example 2 of JP-A-9-251193, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, nucleation was performed in a dispersion medium solution containing a low molecular weight gelatin having a molecular weight of 70,000 to 1,000, and the chemical modification rate of the amino group having a chemical modification rate of 15 to 100%. Even in a light-sensitive material using an emulsion containing tabular grains grown in the presence of a sample, a sample in which the compound represented by the general formula (1) and the fluorosurfactant of the present invention are used is the same as that of Example 1. It was confirmed that the same excellent effect as that of the inventive sample was exhibited.

(Example 23)
In the sample 103 of Example 2 of Japanese Patent Laid-Open No. 2001-100343, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was carried out, even in a photosensitive material using an emulsion containing tabular grains grown in the presence of a dispersion medium in which 40% by mass or more is chemically modified gelatin or low molecular weight gelatin, It was confirmed that the sample in which the compound represented by the general formula (1) and the fluorosurfactant of the present invention were used in combination showed the same excellent effect as the sample of the present invention of Example 1.

(Example 24)
In Sample 305 of Example 3 of Japanese Patent Laid-Open No. 2001-281780, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, the compound represented by the general formula (1) and the fluorosurfactant of the present invention were also used in a photosensitive material using an emulsion containing gelatin containing a large amount of high molecular weight components. It was confirmed that the sample using a combination of these exhibited the same excellent effect as the sample of the present invention of Example 1.

(Example 25)
In Sample 203 of Example 3 of JP-A-3-39946, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, the compound represented by the general formula (1) and the fluorosurfactant of the present invention were also used in a photosensitive material using a tabular emulsion containing mercaptobenzthiazole compounds. It was confirmed that the sample using the combination exhibited excellent effects similar to those of the inventive sample of Example 1.

(Example 26)
In Sample 001 of Example 1 of Japanese Patent Laid-Open No. 2001-75242, the 16th layer of Example 1 was formed instead of the second protective layer. When the same evaluation as in Example 1 was performed, the compound represented by the general formula (1) and the fluorine of the present invention were also used in a photosensitive material capable of high-sensitivity and faithful color reproduction with as little green tint as possible. It was confirmed that the sample combined with the system surfactant showed the same excellent effect as the sample of the present invention of Example 1.

  The silver halide photographic light-sensitive material of the present invention is excellent in storage stability due to less desensitization failure of the light-sensitive material due to adhesion of water-insoluble matter in the developing solution. In particular, there is little decrease in sensitivity when stored under high humidity. Therefore, the silver halide photographic light-sensitive material of the present invention is expected to be used in various fields.

Claims (5)

In the silver halide photographic material having one or more layers including at least one photosensitive layer on the support, at least one of the following layers formed on the support: A silver halide comprising a compound represented by the general formula (1) and containing a fluorosurfactant in at least one of the layers formed on the support. Photosensitive material.
General formula (1)
^{_{R 1 -L-C m H 2m}} -Z
[Wherein, R ¹ represents a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms or a substituted or unsubstituted alkenyl group, and L represents —O—, —NH—, —COO—, or —CONH— . . m represents an integer of 2 to 6. Z represents OSO ₃ M or SO ₃ M, and M represents an alkali metal, a hydrogen atom, ammonium or alkylammonium. ] The silver halide photographic light-sensitive material according to claim 1, wherein the fluorosurfactant is a compound represented by any one of the following general formulas (2A) to (2D).
General formula (2A)

[Wherein, R ^A1 and R ^A2 each independently represents a substituted or unsubstituted alkyl group, and at least one of R ^A1 and R ^A2 represents an alkyl group substituted with a fluorine atom. R ^A3 , R ^A4 and R ^A5 each independently represent a hydrogen atom or a substituent, L ^A1 , L ^A2 and L ^A3 each independently represent a single bond or a divalent linking group, and X ⁺ represents a cationic substituent. Represents a group. Y ⁻ represents a counter anion, but Y ⁻ may not be present when the charge is 0 in the molecule. m ^A represents 0 or 1. ]
General formula (2B)

[Wherein, R ^B3 , R ^B4 and R ^B5 each independently represent a hydrogen atom or a substituent. A and B each independently represent a fluorine atom or a hydrogen atom. n ^B3 and n ^B4 each independently represents an integer of 4 to 8. L ^B1 and L ^B2 each independently represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group formed by combining these. m ^B represents 0 or 1. M represents a cation. ]
General formula (2C)

[Wherein R ^C1 represents a substituted or unsubstituted alkyl group, and R ^CF represents a perfluoroalkylene group. A represents a hydrogen atom or a fluorine atom, and L ^C1 represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group formed by combining these. One of Y ^C1 and Y ^C2 represents a hydrogen atom, and the other represents -L ^C2 -SO ₃ M, and L ^C2 represents a single bond or a substituted or unsubstituted alkylene group. M represents a cation. ]
General formula (2D)
[Rf ^D- (L ^D ) _nD ] _mD -W
[Wherein Rf ^D represents a perfluoroalkyl group, L ^D represents an alkylene group, W represents an anionic group, a cationic group, a betaine group or a nonionic polar group necessary for imparting surface activity. Represents a group having n ^D represents an integer of 0 or 1, m ^D represents an integer of 1-3. ]   The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the compound located at the furthest position from the support on the side having the photosensitive layer contains the compound represented by the general formula (1). .   The halogenation according to any one of claims 1 to 3, wherein the fluorine-containing surfactant is contained in the same layer as the layer containing the compound represented by the general formula (1). Silver photographic material.   The silver halide photographic light-sensitive material according to any one of claims 1 to 4, wherein the silver halide photographic light-sensitive material is a silver halide color photographic light-sensitive material.